Organic/inorganic composite

ABSTRACT

The present invention provides an organic/inorganic composite containing an inorganic phase dispersed in an organic polymer, the inorganic phase comprises one or more metal atoms that are coordinated to at least one rare earth metal atom via oxygen. The composite contains at least 5 mass % of rare earth metal. This rare earth metal is dispersed in the inorganic phase.

RELATED APPLICATIONS

This is a continuation of U.S. patent application Ser. No. 12/659,838,filed Mar. 23, 2010, now U.S. Pat. No. 8,153,026, which was acontinuation of U.S. patent application Ser. No. 11/631,420, filed Jan.3, 2007, now U.S. Pat. No. 7,695,641, which claimed priority tointernational application PCT/JP2005/012617, filed 30 Jun. 2005, whichclaimed priority to Japanese patent applications JP 2004-197711, filed 5Jul. 2004, and JP 2005-36985, filed 14 Feb. 2005. This patentapplication claims the benefit of the priority of all of these priorapplications.

TECHNICAL FIELD

The present invention relates to an organic/inorganic composite that isa composite of a rare earth metal or/and a Period IV transition metaland an organic polymer to be used in fields involving optical functionapplications wherein the transmission, refraction, reflection,polarization plane rotation, and the like of incident light arecontrolled, and functions such as luminescence (fluorescence) due toexcitation by incident light, amplification, and the like are expressed.In addition, the present invention relates to an optical amplifierutilizing the aforementioned organic/inorganic composite wherein theintensity of light of a specific wavelength or bandwidth (opticalsignal) is amplified by light having a different wavelength or bandwidth(excitation light); a light control optical element utilizing theaforementioned organic/inorganic composite wherein the transmission,refraction, focusing, scattering, and the like of light are controlled,while the transmission or absorption of a specific wavelength orbandwidth is also controlled; and a luminescent device utilizing theaforementioned organic/inorganic composite wherein electric energy isconverted to light energy.

BACKGROUND ART

Among the elements listed in the Periodic Table of the Elements, thefollowing are collectively called rare earth metals or rare earthelements: scandium, yttrium, lanthanum, cerium, praseodymium, neodymium,promethium, samarium, europium, gadolinium, terbium, dysprosium,holmium, erbium, thulium, ytterbium, and lutetium. The first practicalapplication of a rare earth metal was the gas mantle invented in the endof the 19th Century wherein cerium was mixed into the luminescencematerial of a gas lamp, which was five-times brighter than conventionalgas lamps. Ever since, the rare earth metals have become indispensablematerials in various fields involving optical function applications suchas the following: red light fluorescent material in televisioncathode-ray tubes (europium, yttrium), x-ray CT scintillators in medicaldiagnosis (gadolinium, praseodymium), light control glasses (neodymium,cerium), solid-state lasers (yttrium, neodymium), electrostaticcapacitors (yttrium, gadolinium); optical fiber amplifier (erbium,praseodymium, terbium, dysprosium), and magneto-optical recording disks(terbium, gadolinium). (For a general review, see Yasuo Suzuki, “Kidoruino Hanashi” [The Story of Rare Earth Elements], Shokabo Publishing Co.,Ltd. 1998.) On the other hand, Period IV transition metals have beenused in a similar manner as fluorescent materials in fluorescent lamps,mercury lamps, and cathode ray tubes. Moreover, because of theirabsorption properties, the transition metals have been used as varioustypes of inorganic pigments, and they have often been used as magneticmaterials as well.

The rare earth metals or/and Period IV transition metals have most oftenbeen used for doping in the form of rare earth metal ions or/and PeriodIV transition metal ions or rare earth metal oxides or/and Period IVtransition metal oxides in a host material. Such host materials includeglasses, garnet crystals, and transparent ceramic materials (zirconiaand the like). However, all such host materials are inorganic, and therehave been almost no examples wherein an organic material has been usedas a host material.

For example, as an example of a light control optical element, a colorfilter multicolor correction lens utilizing absorption and the like havebeen studied. Japanese Patent Application Laid-open No. H 11-133227discloses a process for producing color filter wherein an inorganicpigment is formed into a substrate together with low melting glass fritand then enameled. A simpler means is a method wherein a pigment ismixed directly with an organic medium, and Japanese Patent ApplicationLaid-open No. 2003-4930 and Japanese Patent Application Laid-open No.2004-307853 disclose that a color filter having the required color andtransmission characteristics can be obtained through the use of pigmentfine particles of 100 nm or less in diameter. Although the pigment fineparticles are needed to be dispersed in the organic medium in thesemeans, they can hardly be dispersed without aggregation, which couldlower the optical properties such as transmittance, haze, and the like.

As a means of solving the above problems, Japanese Patent ApplicationLaid-open No. 2004-226913 discloses that the uniform mixing of the(meth)acrylic acid salt of a rare earth metal with an acrylic monomer iseffective for obtaining color correction and the like and a requiredcolor. However, in that method it is necessary to use an acrylic monomeras the organic polymer of the matrix material, and it is impossible toform a composite of colorants in a wide range of organic matrixmaterials.

In addition, if used as a luminescence material, when doping isperformed with a rare earth metal or/and Period IV transition metal at ahigh concentration in an inorganic material, the rare earth metal or/andPeriod IV metal ingredients aggregate or markedly get closer to eachother. As a result, such a process has a problem that it is difficult todope at a high concentration because the phenomenon known as “quenching”occurs wherein the luminescence (fluorescence) is diminished, andessentially, only a maximum concentration of about 100 ppm of rare earthmetal or/and Period IV transition metal can be attained in practice.

On the other hand, organic materials, organic polymers in particular,have excellent properties in terms of processability, light weight, costeffectiveness and the like, and they have become key materialssustaining modern society. Especially in fields involving opticalfunction applications, which are the fields to which the presentinvention is closely related, organic polymers are widely used forplastic lenses in applications such as eyeglasses, contact lenses andthe like (acrylic resin, polycarbonate, cyclic olefin resin and thelike), optical disks (polycarbonate), plastic optical fibers (acrylicresin), and the like (see Fumio Ide, “Oputoerekutoronikusu to KobunshiZairyo” [Optoelectronics and Polymer Materials], Kyoritsu Shuppan Co.,Ltd. 1995). In addition to the doping into inorganic materials such asglasses, garnet crystals, ceramics and the like, the doping of rareearth metals or/and Period IV transition metals, that are used invarious fields involving optical function application, into organicmaterials, especially organic polymers, makes it possible to bring aboutnovel uses that provide better performance than inorganic materials withrespect to processability, light weight, cost effectiveness, and thelike.

However, there has been a problem that it has been impossible tomanufacture materials wherein an organic polymer as a host material isdoped with a rare earth metal or/and Period IV transition metal becauserare earth metals or/and Period IV transition metals are hardlydispersible/soluble in an organic medium.

Optical amplifiers are the number one application wherein rare earthmetals are used. As our advanced information society has become morewidespread, the role of optical communications technology has becomemore important because the amount of data has become increasingly largerand data processing and transmission rates have become increasinglyfaster. Therefore, optical communications networks are being built notonly as main lines in Japan but also on a global scale. In the 1990s thewavelength division multiplexing (WDM) transmission format wherein aplurality of optical signals with different wavelengths are transmittedsimultaneously in a single optical fiber became commercialized, and theconstruction of large capacity high speed data communications networkswas accelerated. One essential basic technology enabling thecommercialization of such a WDM transmission format is opticalamplification technology. In existing commercial optical amplificationtechnology, an optical signal light in the 1550 nm bandwidth is excitedby a semiconductor laser with a wavelength of 980 nm, 1480 nm, and thelike. The optical fiber that carries the optical signal light andexcitation light is doped with a rare earth metal, and after the rareearth metal is excited by the excitation light, the optical signal lightthat has become attenuated due to the long distance transmission processis supplemented by superimposing the light emitted by the rare earthmetal in the 1550 nm band onto the optical signal light. Erbium is themost well-known rare earth metal that is doped into optical fibers, andthe erbium-doped fiber amplifier (EDFA) is widely available forcommercial use. In addition to erbium, the development of opticalamplifiers using rare earth metals such as praseodymium, thulium and thelike in accordance with the optical signal bandwidths used is proceedingvigorously.

In general, rare earth metals are doped in silica glass optical fibersat a concentration of 500 to 1000 ppm. When added at higherconcentrations, the rare earth metal elements aggregate and a phenomenonoccurs wherein the energy of a rare earth metal atom excited by theexcitation light transfers to an adjacent rare earth metal atom beforeemission of the light corresponding to the optical signal wavelength,and thus the desired emission cannot be obtained. This is called“concentration quenching” and delineates the boundary wherein a rareearth metal can be doped into a silica glass optical fiber. As a result,in practice an optical fiber approximately 100 m long is needed toamplify an optical signal to the practically requisite intensity usingexcitation light, and this is a factor limiting the miniaturization ofoptical amplifiers (see Shoichi Sudo, ed., “Erubiumu Tenka Hikari FaibaZofukuki” [Erbium-added Fiber optic Amplifiers], The Optronics Co.,Ltd., 1999, p. 50).

With respect to such optical amplifiers, studies are underway in which,as various types of glass lenses have been replaced by organic polymermolded lenses, conversion of a silica glass matrix material to anorganic polymer matrix material is attempted to make low-cost opticalamplifiers practical and increase their cost effectiveness, which willbe necessary not only for long distance main line fiber optic networks,but also for the massive fiber optic transmission lines of subscribersystems and the like that are becoming more widespread in averagehouseholds (see Japanese Patent Application Laid-open No. H05-088026,Japanese Patent Application Laid-open No. 2000-208851, U.S. Pat. No.6,292,292, U.S. Pat. No. 6,538,805, U.S. Pat. No. 6,751,396, JapanesePatent Application Laid-open No. 2000-256251, and Japanese PatentApplication Laid-open No. H05-179147).

There is a problem, however, because rare earth metals do not easilydissolve or disperse in an organic medium. As a result, it has beenimpossible to dope a rare earth metal into an organic polymer matrixmaterial, which provides excellent cost effectiveness in plastic opticalfibers and the like, and this makes it difficult to improve greater costeffectiveness in optical transmission networks by the practicalapplication of a low cost optical amplifier.

In general, fluorescent materials contain rare earth metals that can belisted as rare earth metals usable for doping organic polymers. Suchfluorescent materials comprise three components, i.e., a host material,an activator, and a co-activator. Crystals of oxides and crystals ofionic compounds are used as the host material (see M. T. Anderson, etal., “Phosphors for Flat Panel Emission Displays,” in B. G. Potter, Jr.et al., eds. Synthesis and Application of Lanthanide-Doped Materials, p.79, The American Ceramic Society 1996). In other words, the goal hasbeen achieved not by directly doping an organic polymer with a rareearth metal having fluorescence itself as the activator, but by firstdoping oxide crystals such as yttrium-aluminum-garnet (YAG) and the likewith a rare earth metal, and then pulverizing the crystals and mixingthem with an organic polymer. However, when such means are used, bakingat a high temperature of about 1400° C. is necessary to form the YAGcrystals, which increases the processing cost. In addition, the particlesize of the pulverized fluorescent materials containing the rare earthmetal are generally 1000 nm (1 μm) or more, and when they are dispersedat a high concentration for the purpose of using them in an opticalamplifier, transparency is decreased due to optical scattering, and theproduct can no longer function as an optical waveguide. Thus, there is aconcentration limitation below which fluorescent materials, prepared bydoping rare earth metals into a host material such as a crystal, can bedispersed in a resin, and it is impossible to achieve both theminiaturization of optical amplifiers by using a high concentration ofdoping agent and an improvement in cost effectiveness by using anorganic material as an optical transmission medium.

As a method of using a host material containing a rare earth metal inthe same way as a fluorescent material, a means wherein the rare earthmetal is carried by fine particles (Japanese Patent ApplicationLaid-open No. 2003-89756) and a means wherein the rare earth metal isembedded in fine particles by ion implantation (L. H. Slooff, et al.,Journal of Applied Physics, Vol. 83, p. 497, 1998) have been proposed,but both involve the problem wherein optical transparency is hinderedbecause of the large size of the fine particles.

On the other hand, as means for doping an organic polymer directly witha rare earth metal, a method for synthesizing an organic/inorganiccomposite has been proposed wherein (a) an organic coordination compoundbetween a rare earth metal and an organic ligand such as a pyridine,phenanthrolene, quinoline, β-diketone or the like is formed initially,and the rare earth metal is dispersed in an organic polymer thereby; and(b) the rare earth metal is contained in an organic cage complexes, andthe inclusion compound is dispersed in an organic polymer; and the like(see L. H. Slooff, et al., Journal of Applied Physics, Vol. 83, p. 497,1998).

Such means illustrated by (a) and (b) above broaden the type of rareearth metal that can be used and the range of concentration. Moreover,the dispersion phase containing the rare earth metal obtained therebyhas molecular order, so even though the dispersion phase may aggregatesomewhat, the size can be limited to a range from roughly a fewnanometers to about 20 nm, and this enables doping at a highconcentration without causing the decrease in transparency thataccompanies optical scattering. There is a problem, however, becausewhen these means are used, the excited state energy in the rare earthmetal that has been excited by the excitation light transfers to themolecular vibrations of the CH and OH groups in the organic cagecomplexes or/and organic ligands, that are directly bonded to the rareearth metal, in accordance with the Franck-Condon principle known fromquantum mechanics, and the emission process specific to the rare earthmetal is inhibited (quenched) thereby (see W. Siebrand, The Journal ofChemical Physics, Vol. 46, p. 440, 1967).

For solving such a problem, a means has been proposed wherein quenchingis suppressed by insuring that the excitation energy level of the rareearth metal and the excitation energy level of the organic ligands ororganic cage complexes do not overlap by either fluorinating ordeuterating the CH groups of the organic ligands of the rare earth metalcoordination compound or organic cage complexes (Y. Hasegawa, et al.,Chemistry Letters, 1999, p. 35 and Hasegawa “Yuki Baitai Chu deHikaranai Neodymium o Donoyouni Hikaraseruka?” [How can we makeneodymium, which does not emit light in an organic medium, emit light?]Kagaku to Kogyo (Chemistry and Chemical Industry), Vol. 53, page 126,2000). Such a means is effective in terms of suppressing quenching whileenabling a rare earth metal to be dissolved or dispersed in an organicmedium at a high concentration. However, the problem remains that thefluorides and deuterides used as a starting material are very expensive,and therefore such a means cannot bring about the effect of improvingthe cost effectiveness of optical transmission networks that can beexpected to accompany the practical application of optical amplifiershaving an organic polymer as a matrix material.

A light control optical element can be listed as a second applicationusing a rare earth metal. Light can be sensed by human eyes via variousoptical elements that control the transmission, refraction, focusing,scattering and the like of light. Many kinds of optical elements can belisted such as the lenses used in eyeglasses, the covers and lightingwindows used in various lighting devices, the optical filters used intelevision receivers, the windows and lenses used in goggles inindustrial processes such as welding and in medical therapy, and so on.A variety of optical elements, not only limited to the examplesdescribed above, have the important function of controlling thetransmission, refraction, focusing, scattering and the like of light invarious kinds of optical instruments. Such optical elements generallyhave a high transparency in the visible wavelength range. However, manyother optical elements are also used to control transmission orabsorption of both natural and artificial light such as light controllenses, light control glasses, and the like, and, as a group, suchelements are called light control optical elements.

Among the lenses for eyeglasses in the examples noted above, lenses forsunglasses, used for the reduction of sickening glare by decreasinglight intensity, is the most typical example of a light control opticalelement. In particular, lenses for sunglasses with a high antiglareeffect can be obtained by reducing the amount of light at wavelengths of400 to 500 nm. As part of the discussion of lenses for eyeglasses, thereare persons who have a visual disorder characterized by difficulty indistinguishing colors because they have a congenital visual sensitivitycurve that is different from the visual sensitivity curve of normalpersons, and for such persons there are corrective lenses that adjustthe transmittance value of light to match the visual sensitivity of theperson having the visual disorder by selectively amplifying theabsorption of light at specific wavelengths. Among the lighting windowsor covers listed above, windows and covers with a strong antiglareeffect can be obtained for lights having halogen lamps such as thoseused in automobile headlights and the like by controlling thetransmittance of a light at wavelengths of 560 to 600 nm.

Thus, means wherein a material forming an optical element is doped withvarious light absorbing materials such as pigments and the like areknown as means for controlling the transmission or absorption of lightof a specific wavelength or wavelength band. Among them, the elementslisted above and generally called rare earth metals or rare earthelements or/and Period IV transition metals of vanadium, chromium,manganese, iron, cobalt, nickel and copper, are known to be excellent asdoping materials for controlling the transmission or absorption of lightof a specific wavelength or waveband in accordance with the use orrequired purpose, because each element presents a sharp and largeabsorption spectrum at a particular waveband. With respect to theinventions utilizing the features of these rare earth metals or/andPeriod IV transition metals, there are many applications such as thefollowing: contrast reinforced glasses and a lens using the same whereinglass is doped with neodymium oxide (Nd2O3) (Japanese Patent ApplicationLaid-open No. H08-301632, U.S. Pat. No. 6,604,824) and windows using thesame (U.S. Pat. No. 6,416,867); automobile headlights (U.S. Pat. No.5,961,208); an optical filter (U.S. Pat. No. 4,106,857) wherein glass isdoped with various rare earth elements such as holmium, praseodymium,dysprosium, or the like.

On the other hand, as materials constituting various optical elementsthat control the transmission, refraction, focusing, and scattering oflight and the like, polymer materials with excellent processability,cost effectiveness and light weight have become widespread, and havebecome indispensable materials technology for modern society, as in thefield of light weight lenses for eyeglasses, lenses for optical diskdevices and the like. Therefore, in the field of light control opticalelements doped with a rare earth metal or/and Period IV transition metalsuch as those in the preceding paragraph are needed, there is a demandfor such elements utilizing polymer materials.

However, rare earth metals or/and Period IV transition metals have theproperty of dissolving or dispersing very poorly in organic media, andtherefore the practical application of light control optical elementshaving a polymer matrix material that express light transmission andabsorption properties specific to rare earth elements has been inhibitedthereby.

To resolve such a problem the following means for synthesizing anorganic/inorganic composite have been proposed in the past: (a) acoordination compound between a rare earth metal or/and Period IVtransition metal and an organic ligand such as a pyridine,phenanthrolene, quinoline, β-diketone or the like is initially formed,and then the rare earth metal or/and Period IV transition metal isdispersed in an organic polymer thereby; (b) a rare earth metal or/andPeriod IV transition metal is included in an organic cage complexes, andthe inclusion compound is dispersed in an organic polymer; (c) a polymeris formed using a polymer synthesizing monomer of a rare earth metalor/and Period IV transition metal; and the like.

When methods (a) and (b) are used, however, absorption in the UV regiondue to the organic ligands or organic cage complexes tends to increase,and this induces an energy transfer from the organic ligands or organiccage complexes to the matrix material polymer, and UV light degradationof the matrix material polymer by the generation of radicals formed uponcleavage of the molecular chains in the organic ligands or organic cagecomplexes and the like. In addition, the cost of the starting materialsof most such organic ligands or organic cage complexes is high, and thehigh cost effectiveness that is the feature of a polymer optical elementis impaired.

As an example of method (c), a method is known wherein a (meth)acrylicacid rare earth metal salt, hydroxyalkyl (meth)acrylate and phthalicacid, and a monomer copolymerizable with these are mixed, and themixture is polymerized to produce a polymer (see Japanese PatentApplication Laid-open No. 2004-226913). There is a problem, however,because when this method is used, the polymer material that can be usedas a matrix is limited to a very small number of polymers such asacrylic resins, styrene resins, and the like, and it is impossible tosatisfy the need for polymeric optical elements wherein various polymermaterials such as polycarbonate resins, cyclic olefin resins, polyesterresins, epoxy resins and the like have been developed as a matrix.

A luminescent device can be listed as a third application using a rareearth metal. Ever since Edison invented the incandescent bulb in the endof the 19th Century, various electric lamps and discharge tubesrepresented by fluorescent lamps have made major contributions to lifein society. In the 1960s, light emitting diodes (LEDs) comprisingcompound semiconductors such as gallium arsenide and the like becamepractical, and they became widespread as miniature light emittingelements of infrared light, red light, green light and the like. Theoptical device of the present invention is a device that convertselectric energy to light energy, as typified by various electric bulbs,discharge tubes, LED devices and the like. More specifically, as shownin FIGS. 14( a) to 14(c), the electric energy is converted by a lightemitting element to light energy, which in turn is reconverted to lightat a wavelength suitable for the application thereof by a fluorescentmaterial containing a rare earth metal that is excited by the lightemitted from this light emitting element. Thus, even when the lightemitting element itself is one wherein, for example, electric energy isconverted to UV light, it becomes possible to obtain light of thevarious wavelengths peculiar to each of the rare earth metals becausethis UV light excites the fluorescent material containing the rare earthmetal.

Generally speaking, an LED comprising a compound semiconductor such asgallium arsenide, gallium phosphide and the like is known to have ahigher luminous efficiency (conversion efficiency from electric energyto light energy) than an incandescent electric bulb or discharge tubes.The emission of red light can be obtained from compound semiconductorssuch as gallium arsenide, gallium arsenide phosphide and the like; theemission of red to yellow light can be obtained from aluminum indiumgallium phosphide; and the emission of green light can be obtained fromgallium phosphide. These lights are used in light emitting indicators ofvarious types of electronic equipment, light emitting elements forremote control devices that operate various electronic equipment, LEDdisplay modules, and the like. In addition, recently a blue LED has beenrealized by the invention of a gallium nitride LED, and full color,large screen displays integrating various LEDs emitting the threeprimary colors of red, green and blue have been put into practical uses.Thus, as LEDs have extensively used from a point light source to a flatpanel light source, there arises a vigorous movement in which lightsthat heretofore have been dependent on incandescent bulbs and dischargetubes are replaced by LEDs. Especially, the use of LEDs, which have aconversion efficiency from electric energy to light energy much higherthan that of glass tube incandescent bulbs and discharge tubes, is aneffective means to promote energy savings today when the problem ofglobal warming has become severe. In Japan, the technologicaldevelopment of the use of LEDs has been promoted by the “Project for theDevelopment of Compound Semiconductors for High EfficiencyOptoelectronic Conversion” (nicknamed: “Light of the 21st CenturyProject”) established by the Ministry of Economy, Trade and Industry in1998. In the course of such technical development a white LED has beendeveloped, and LEDs are becoming more widespread as a light source forlamps in place of incandescent bulbs and discharge tubes.

There are three methods for obtaining a white LED: (1) Obtaining whiteas a mixed color by integrating red, green and blue LEDs; (2) Obtainingwhite as a mixed color of yellow and blue by generating blue light witha blue LED and simultaneously generating yellow fluorescent light byexciting a fluorescent material with the blue light; and (3) Obtainingwhite by exciting three types of fluorescent materials that emit red(R), green (G), and blue (B) using a blue LED or an ultraviolet LED, andthen combining the three primary colors R, G, and B (Tsunemasa Taguchi,ed. “Hakushoku LED Shomei System no Kokido/Kokoritsu/Chojumyoka Gijutsu”[Technology for High Intensity/High Efficiency/Long Life White LEDLighting Systems] Gijutsu Joho Kyokai, 2003).

If method (1) is used, a drive circuit for each of the three colors mustbe provided because the operating characteristics of the LEDscorresponding to each of the three colors are different, and this willinterfere with miniaturization, less power consumption and the like, andtherefore methods (2) and (3) are considered more practical.

Incidentally, it is known that the background of achieving white lightthat is excellent in intensity and color rendering properties in varioustypes of incandescent and discharge tubes was originated from the use ofa rare earth metal as a luminescence material. It is said that the firstpractical application of a rare earth metal was the gas mantle inventedin the end of the 19th Century wherein cerium was mixed into theluminescence material of a gas lamp, which was five-times brighter thanconventional gas lamps, and rare earth metals such as cerium (Ce),neodymium (Nd), and europium (Eu) have come to be used in incandescentand discharge tubes. Therefore, even when methods (2) and (3) are used,it is preferable to use these rare earth metals as luminescencematerials that are excited by blue light or UV light. However, for usinga rare earth metal as a luminescence material, as shown in FIG. 14( c),the general construction of the LED must be sealed with a resin afterthe light emitting element 31 (in this case, an LED chip) is mounted ona substrate. If the desired rare earth metal 33 such as Ce, Tb, Eu andthe like, which are luminescence materials, can be dispersed in theresin as shown in FIG. 14( c), white light can be obtained as a mixedcolor with the fluorescent light 34 emitted from the rare earth metal 33that has been excited by the light 32 emitted from the LED. There is aproblem, however, because the rare earth metal does not easily dissolvein an organic medium such as the LED sealing resin 35.

To overcome this kind of problem, a fluorescent material containing arare earth metal has been used in the past in display applications suchas television receivers, flat panel displays and the like, because itwill disperse the rare earth metal uniformly in an organic medium suchas the LED sealing resin 35 and the like. Such fluorescent materialscomprise three components, i.e., a host material, an activator, and aco-activator. Crystals of oxides and crystals of ionic compounds areused as the host material (see M. T. Anderson, et al., “Phosphors forFlat Panel Emission Displays,” in B. G. Potter, Jr. et al., eds.Synthesis and Application of Lanthanide-Doped Materials, p. 79, TheAmerican Ceramic Society 1996). In other words, the goal has beenachieved not by directly doping an LED sealing resin with a rare earthmetal itself, which is a luminescence material, but by first dopingoxide crystals such as yttrium-aluminum-garnet (YAG) and the like with arare earth metal, and then pulverizing the crystals and mixing them witha resin.

However, when such a means is used, baking at a high temperature ofabout 1400° C. is necessary to form the YAG crystals, which increasesthe processing cost. In addition, the particle size of the pulverizedfluorescent material containing the rare earth metal generally has alower limit ranging from 1000 nm (1 μm) to several hundred nanometers,and when the particles are dispersed at a high concentration,transparency is decreased due to optical scattering that cannot beignored. Thus, there is a concentration limitation below whichfluorescent materials, prepared by doping rare earth metals into a hostmaterial such as a crystal, can be dispersed in a resin, and it isimpossible to vary the dispersion concentration freely over a widerange.

As means for solving such a problem originating in fluorescent materialsthat have been used in the past and doping an organic medium directlywith a rare earth metal, an organic/inorganic composite synthesis meanshas been proposed wherein (a) a coordination compound between a rareearth metal and an organic ligand such as a pyridine, phenanthrolene,quinoline, β-diketone or the like is formed, and the rare earth metal isdispersed in an organic medium thereby; and (b) the rare earth metal isincluded in an organic cage complexes, and the inclusion compound isdispersed in an organic medium; and the like.

Such means illustrated by (a) and (b) above involve broadening the typeof rare earth metal and the range of concentration limitations. There isa problem, however, because when these means are used, the excited stateenergy in the rare earth metal that has been excited by blue lighttransfers to the molecular vibrations of the CH and OH groups in theorganic cage complexes and the organic ligand that is directly bonded tothe rare earth metal due to the Franck-Condon principle known in quantummechanics, and the emission process specific to the rare earth metal isinhibited (quenched) (see W. Siebrand, The Journal of Chemical Physics,Vol. 46, p. 440, 1967, and L. H. Slooff, et al., Journal of AppliedPhysics, Vol. 83, p. 497, 1998).

For solving such a problem, a means has been proposed wherein quenchingis suppressed by insuring that the excitation energy level of the rareearth metal and the excitation energy level of the organic ligands ororganic cage complexes do not overlap by either fluorinating ordeuterating the CH groups of the organic ligand of the rare earth metalcoordination compound or organic cage complexes (Japanese PatentPublication No. 10-36835, Japanese Patent Application Laid-open No.2000-256251, Y. Hasegawa, et al., Chemistry Letters, 1999, p. 35 andHasegawa “Yuki Baitai Chu de Hikaranai Neodymium o DonoyoniHikaraseruka?” [How can we make neodymium, which does not emit light inan organic medium, emit light?] Kagaku to Kogyo (Chemistry and ChemicalIndustry) Vol. 53, page 126, 2000). Moreover, a luminescent device usinga rare earth metal coordination compound obtained thereby has beenproposed (Japanese Patent Application Laid-open No. 2003-81986, JapanesePatent Application Laid-open No. 2003-147346). Such a means is effectivein terms of suppressing quenching while enabling a rare earth metal tobe dissolved or dispersed in an organic medium at a high concentration.However, the problem remains that because the fluorides and deuteridesused as a starting material are very expensive, such a means lacks thecost effectiveness required by LED illumination, and this prevents thesame from becoming widespread as consumer appliances.

DISCLOSURE OF THE INVENTION

As noted above, an organic/inorganic composite wherein an organicpolymer is doped by various methods with a rare earth metal or/andPeriod IV transition metal has been proposed. However, there is no knownmaterial that can manifest optical functions while satisfying allconditions of doping with a rare earth metal or/and Period IV transitionmetal at a high concentration, suppressing quenching, assuring opticaltransparency, and also assuring processability, light weight, and costeffectiveness that are the properties of a polymer-based opticalelement, and inhibiting the degradation of the polymeric matrix materialcaused by absorption in the UV range.

With the foregoing in view, an object of the present invention is toprovide an organic/inorganic composite wherein doping at a highconcentration is performed using a rare earth metal or/and Period IVtransition metal, and both the requirements for suppressing quenchingand assuring optical transparency are satisfied. A second object of thepresent invention is to provide an optical amplifier utilizing anorganic/inorganic composite containing a rare earth metal, which make itpossible (1) to dope rare earth metals at high concentrations, (2) tosuppress quenching, (3) to assure high transparency, and (4) to improvecost effectiveness. A third object of the present invention is toprovide a light control optical element used for controllingtransmittance and absorbance of light at a specific wavelength or inspecific wavelength region utilizing an organic/inorganic compositecontaining a rare earth metal or/and Period IV transition metal, whichmake it possible (1) to dope rare earth metals or/and Period IVtransition metals at high concentrations, (2) to avoid UV-induceddegradation of the polymer matrix, and (3) to assure excellentprocessability, light weight, and cost effectiveness. A fourth object ofthe present invention is to apply an organic/inorganic composite to afluorescent material in a luminescent device that converts electricenergy to light energy, which make it possible (1) to dope rare earthmetal luminescence material at high concentrations, (2) to suppressquenching, (3) to assure optical transparency, and (4) to assure costeffectiveness. In particular, an object thereof is to provide aluminescent device having an LED with high luminous efficiency, colorappearance, and excellent cost effectiveness as the light emittingelement.

We performed diligent research to attain the above objects. As a result,we discovered that by coordinating a rare earth metal or/and Period IVtransition metal with other metal(s) via an oxygen atom(s), not only canan organic polymer be doped with metal species at a high concentration,but also that quenching due to energy transfer between atoms of the rareearth metal or/and Period IV transition metal, and/or between atoms ofthe rare earth metal or/and Period IV transition metal and the CH and OHgroups can be controlled thereby. In addition, we discovered that bycontrolling the diameters in the dispersion phase containing a rareearth metal or/and Period IV transition metal linked to other metal(s)via an oxygen atom(s), the optical transparency of a transparent organicpolymer can be assured, thus completing the present invention. On theone hand, we discovered that by applying the organic/inorganic compositeof the present invention, the aforementioned second object can beattained. More specifically, the optical amplifier of the presentinvention comprises an inorganic dispersion phase wherein a rare earthmetal is coordinated to other metal(s) via an oxygen atom(s), and thisinorganic dispersion phase is used by forming a composite thereof withan organic polymer. In addition, the inventors discovered that byapplying the aforementioned organic/inorganic composite, theaforementioned third object can be attained. More specifically, thelight control optical element of the present invention is a lightcontrol optical element which utilizes a rare earth metal or/and PeriodIV transition metal-containing organic/inorganic composite wherein anorganic polymer is used to form a composite thereof with an inorganicdispersion phase, in which other metal(s) is (are) coordinated to a rareearth metal or/and Period IV transition metal via an oxygen atom(s).High concentration doping with the rare earth metal or/and Period IVtransition metal is attainable thereby. Furthermore, even though theabsorption of the rare earth metal or/and Period IV transition metallies in the UV wavelength range, the excitation energy of the rare earthmetal produced by absorption of UV light is not transferred to thepolymeric matrix material via the ligand of the present inventionwherein other metal(s) is (are) coordinated via an oxygen atom(s), andradical generation accompanied by the cleavage of the ligand itself doesnot occur. In addition, the starting materials required for working ofthe present invention are easily obtained and economically efficient,and because doping of the rare earth metal or/and Period IV transitionmetal in various polymeric matrix materials is enabled thereby, the costeffectiveness, processability and light weight, which are the featuresof a polymeric optical element, are not lost.

We also discovered that by applying the organic/inorganic composite ofthe present invention the aforementioned fourth object can be attained.More specifically, in the luminescent device of the present invention,the inorganic dispersion phase comprising a rare earth luminescencematerial wherein other metal(s) is (are) coordinated to a rare earthmetal via an oxygen atom(s) is used by forming a composite thereof withan organic polymer.

In other words, the organic/inorganic composite of the present inventionhas the structure described below.

1. An organic/inorganic composite in which at least one species of rareearth metals or/and Period IV transition metals is dispersed in anorganic polymer, the composite having an inorganic dispersion phase inwhich one or more other species of metals are coordinated to the atleast one species of rare earth metals or/and Period IV transitionmetals via oxygen.

In accordance with the above constitution, high concentration doping invarious organic polymers can be achieved by coordinating other metal(s)with a rare earth metal or/and Period IV transition metal via an oxygenatom(s), and specific absorption capability is imparted thereby to theorganic polymer.

In addition, because the other metal(s) is (are) coordinated via anoxygen atom(s), quenching due to energy transfer between the rare earthmetal and the CH and OH groups of the organic polymer is inhibited.Concurrently, the metal coordinated via an oxygen atom(s) suppressesquenching accompanied by proximity interactions, and/or clusterformation of the rare earth metal or/and Period IV transition metal.Applications of coordination compounds intended for the dispersion of arare earth metal in an organic polymer are also described in theaforementioned prior art, and generally speaking, coordination to anorganic compound is performed via an oxygen or nitrogen atom capable ofcoordination to a metal. However, quenching due to energy transferbetween the rare earth metal and the CH and OH groups of the organicpolymer noted above cannot be inhibited by coordination using an organiccompound as a ligand. If coordination to the other metal(s) via anoxygen atom(s) is not performed, aggregation will occur among the atomsof the rare earth metal/and Period IV transition metal, and essentiallydispersion in the organic polymer cannot occur. Even if dispersion atdilute concentrations were possible, it would be impossible to form adesired organic/inorganic composite containing a rare earth metal/andPeriod IV transition metal due to quenching accompanied by proximityinteractions, and/or cluster formation among the atoms of the rare earthmetal/and Period IV transition metal. In the present invention, the rareearth metal/and Period IV transition metal is coordinated via an oxygenatom(s) that is bonded to the other metal(s). The inorganic dispersionphase of the present invention is represented schematically in FIG. 1.As shown in the drawing, the rare earth metal/and Period IV transitionmetal-containing organic/inorganic composite of the present invention isformed by a composite containing an inorganic dispersion phasecomprising a rare earth metal or/and Period IV transition metal 1 withwhich other metals 2 are coordinated thereto via an oxygen atom(s), andan organic polymer that is not shown in the drawing. What is importantin the aforementioned inorganic dispersion phase is that the distancebetween the same species of rare earth metals/and Period IV transitionsmetals are kept to be apart by the ligands coordinated via oxygen atoms.Therefore, the number and type of ligands comprising oxygen and anothermetal are not fixed, and the present invention is not strictly limitedstoichiometrically to the kind of molecular structure shown in FIG. 1.

When used as an optical material and the like, it is desirable that theorganic polymer of the present invention have optical transparency(permeability). The transmittance value of the organic polymer is notparticularly limited provided it is within a range having transparency,but a transmittance value of 30% to 100% is preferable, and a range of80% to 100% is even more preferable. In addition, the rare earthmetal/and Period IV transition metal-containing organic/inorganiccomposite of the present invention can take the form of an associationstructure provided that the distance between the same species of rareearth metals/and Period IV transition metals are kept to be apart.

In FIG. 1, R represents an alkyl group, alkylcarbonyl group such as anacetyl group and the like, or hydrogen and the like.

2. An organic/inorganic composite, which is an organic/inorganiccomposite having a rare earth metal/and Period IV transition metal, theorganic/inorganic composite having an inorganic dispersion phase inwhich one or more other species of metals are coordinated to the rareearth metal/and Period IV transition metal via oxygen, the inorganicdispersion phase having an average particle diameter of 0.1 to 1000 nm.

In accordance with the above constitution, the average diameter of therare earth metal/and Period IV transition metal dispersion phase inwhich other metal(s) is(are) coordinated to the aforementioned rareearth metal/and Period IV transition metal via an oxygen atom(s) lieswithin the aforementioned range, and excellent transparency of theorganic/inorganic composite is assured thereby, because said diameter isrelatively small in comparison with the wavelengths of light passingthrough the rare earth metal-containing organic/inorganic composite.

3. An organic/inorganic composite, wherein a proportion of a rare earthmetal/and Period IV transition metal is 90 mass % or less, as calculatedin terms of solid content, based on a total mass of an organic polymerand an inorganic dispersion phase in which other species of metals arecoordinated to the rare earth metal/and Period IV transition metal viaoxygen.

In accordance with the above constitution, a high level of opticaltransmission can be expressed in fields involving optical functionapplications with which the present invention is closely related, sincethere is no scattering loss of light due to secondary aggregation of therare earth metal/and Period IV transition metal that is coordinated toother metal(s) via an oxygen atom(s). Thus, if the proportion of therare earth metal/and Period IV transition metal, calculated as solids,is 90 mass % or less based on the total mass of the organic polymer andthe inorganic dispersion phase comprising other metal(s) coordinated tothe aforementioned rare earth metal/and Period IV transition metal viaan oxygen atom(s), the object of the present invention can be attained,and the need will arise to control absorption of the wavelengths oflight that pass through the organic/inorganic composite depending on therequired use of the organic/inorganic composite obtained in the presentinvention. As a result, the proportion of the rare earth metal/andPeriod IV transition metal, calculated as solids, is preferably 30 mass% or less based on the total mass of the organic polymer and theinorganic dispersion phase comprising other metal(s) coordinated to theaforementioned rare earth metal/and Period IV transition metal via anoxygen atom(s).

4. An organic/inorganic composite, wherein a metal coordinated to a rareearth metal/and Period IV transition metal via oxygen is one or morespecies of elements selected from Group 3B, Group 4A, and Group 5Ametals.

In accordance with the above constitution, coordination of the othermetal(s) with the rare earth metal/and Period IV transition metal via anoxygen atom(s) will be facilitated, and effective dispersion into theorganic polymer and effective suppression of quenching during the lightemission process of the rare earth metal/and Period IV transition metalcan be realized thereby.

5. An organic/inorganic composite, wherein an inorganic dispersion phasehaving a rare earth metal/and Period IV transition metal and otherspecies of metals coordinated thereto via oxygen is prepared from a saltof the rare earth metal/and Period IV transition metal and an alkoxideof other species of metals.

In accordance with the above structure, the dispersion phase wherein theother metal(s) coordinates to the rare earth metal/and Period IVtransition metal via an oxygen atom(s) can be formed efficiently.

As noted above, the organic/inorganic composite of the present inventionhas a structure comprising: a dispersion phase comprising a rare earthmetal/and Period IV transition metal coordinated to other metal(s) viaan oxygen atom(s); and an organic polymer. As a result, the presentinvention accomplishes the effect of providing an organic/inorganiccomposite wherein: a rare earth metal/and Period IV transition metal canbe doped at a high concentration; color rendering properties dependenton the absorption of the doping metal are imparted in a state whereinoptical transparency is assured; and quenching suppression and opticaltransparency are achieved.

6. An optical amplifier having an optical waveguide for transmittinglight of a specific wavelength or waveband (signal light) and lighthaving a different wavelength or waveband therefrom (excitation light),in which intensity of the signal light is amplified by the excitationlight, wherein the optical waveguide is the organic/inorganic compositeaccording to item 1.

In accordance with the above structure, high concentration doping of therare earth metal in the organic polymer can be achieved by coordinatingthe rare earth metal with the other metals via an oxygen atom(s). Inaddition, by coordinating the other metals via an oxygen atom(s),quenching due to the energy transfer between the rare earth metal andthe CH and OH groups of the organic polymer is suppressed. Concurrently,concentration quenching due to the proximity interactions or/and clusterformation of the rare earth metal is also suppressed thereby.

Use of a coordination compound for the purpose of dispersing rare earthmetals in an organic polymer is described in the aforementioned priorart, and in general this prior art coordination to an organic compoundis performed via an oxygen or nitrogen capable of coordination to ametal. However, the quenching due to energy transfer between the rareearth metal and the CH and OH groups of the organic polymer noted abovecannot be controlled by coordination wherein an organic compound is usedas a ligand.

If coordination with the other metals via an oxygen atom(s) is notperformed, aggregation of the rare earth metals will occur, andessentially dispersion in the organic polymer cannot be achieved. Evenif dispersion at dilute concentrations were possible, it would beimpossible to form an organic/inorganic composite containing theintended rare earth metal due to quenching that accompanies proximityinteractions and/or cluster formation among the atoms of the rare earthmetal.

When used as an optical a material and the like, it is desirable thatthe organic polymer of the present invention have optical transparency(permeability). Although the transmittance of the organic polymer is notlimited to a specific range provided that it is substantiallytransparent, a transmittance of 30% to 100% is preferable, and a rangeof 80% to 100% is even more preferable.

In addition, the inorganic dispersion phase containing a rare earthmetal of the present invention can take the form of an associationstructure provided that the distance between the same species of rareearth metals are kept to be apart.

In the optical amplifier of the present invention, the average particlesize of the inorganic dispersion phase as a whole wherein another metalis coordinated to a rare earth metal via an oxygen atom(s) preferablyranges from 0.1 to 1000 nm. Excellent transparency of theorganic/inorganic composite containing a rare earth metal is assuredthereby because the particle size is relatively small in comparison withthe wavelength of light propagating in the organic/inorganic compositecontaining a rare earth metal.

In the optical amplifier of the present invention, the content of rareearth metals in terms of solid content is preferably 90 mass % or lessof the total mass of the organic polymer and the inorganic dispersionphase wherein another metal is coordinated to the aforementioned rareearth metal via an oxygen atom(s). A high level of optical transmissioncan be expressed in fields involving optical function applications withwhich the present invention is closely related without bringing aboutscattering loss of light due to secondary aggregation of the rare earthmetal that is coordinated to another metal via an oxygen atom(s). Thus,if the ratio of rare earth metal when mathematically converted to solidcontent is 90 mass % or less of the total mass of the organic polymerand the inorganic dispersion phase wherein another metal is coordinatedto the aforementioned rare earth metal via an oxygen atom(s), the objectof the present invention can be attained thereby, and because the needwill arise to control absorption of the wavelength of light passingthrough the organic/inorganic composite containing a rare earth metal inaccordance with the use of the organic/inorganic composite obtained inthe present invention, the ratio of rare earth metal when mathematicallyconverted to solid content is preferably 30 mass % or less of the totalmass of the organic polymer and the inorganic dispersion phase whereinanother metal is coordinated to the aforementioned rare earth metal viaan oxygen atom(s).

In the optical amplifier of the present invention, the metal coordinatedto the rare earth metal via an oxygen atom(s) is preferably one or morethan one element selected from a group consisting of Group 3B, Group 4A,and Group 5A metals. Coordination of the other metal with the rare earthmetal via an oxygen atom(s) will be facilitated thereby, and effectivedispersion into the organic polymer and effective suppression ofquenching during the light emission process of the rare earth metal canthus be realized.

In the optical amplifier of the present invention, the inorganicdispersion phase wherein a rare earth metal is coordinated to anothermetal via an oxygen atom(s) is preferably formed by a rare earth metalsalt and an alkoxide of the other metal. In accordance with the abovestructure, the dispersion phase wherein the other metal coordinates withthe rare earth metal via an oxygen atom(s) can be formed efficiently.

As noted above, the optical amplifier of the present invention has anoptical waveguide wherein light of a specific wavelength or waveband(signal light) and light having a different wavelength or wavebandtherefrom (excitation light) is transferred thereby, and also has astructure comprising a dispersion phase containing a rare earth metalwherein another metal is coordinated to the rare earth metal via anoxygen atom(s); and an organic polymer.

As a result, the present invention: (1) enables high concentrationdoping of a rare earth metal (2) suppresses quenching and (3) can assureoptical transparency. In addition, because the present invention doesnot require expensive starting materials such as fluorides anddeuterides to control quenching and a high temperature process to form ahost material such as oxide crystals and the like, it provides theeffect of (4) realizing a assure of cost effectiveness.

7. A light control optical element having the organic/inorganiccomposite according to item 1.

In accordance with the above structure, high concentration doping of theorganic polymer can be achieved by coordinating a rare earth metalor/and Period IV transition metal with another metal via an oxygenatom(s). In addition, because the other metal is coordinated via anoxygen atom(s), the present invention inhibits the energy transferbetween the atoms of the rare earth metal and the CH and OH groups ofthe organic polymer.

With respect to the use of the coordination compound for the purpose ofdispersing the rare earth metal or/and Period IV transition metal in theorganic polymer, as described in the aforementioned prior art, generallyspeaking coordination with an organic compound is performed via anoxygen or nitrogen atom capable of coordination with a metal. However,energy transfer between the rare earth metal or/and Period IV transitionmetal and the CH and OH groups of the aforementioned organic polymernoted above cannot be inhibited by coordination using an organiccompound as a ligand.

When used as an optical material and the like, it is desirable that theorganic polymer of the present invention have optical transparency(permeability). The transmittance value of the organic polymer is notparticularly limited provided it is within a range having transparency,but a transmittance value of 30% to 100% is preferable, and a range of80% to 100% is even more preferable.

The light control optical element of the present invention may have astructure wherein the average particle size of the inorganic dispersionphase as a whole wherein another metal is coordinated thereto via anoxygen atom(s) ranges from 0.1 to 1000 nm.

In accordance with the above structure, the average particle size of theinorganic dispersion phase as a whole wherein another metal iscoordinated to the aforementioned rare earth metal or/and Period IVtransition metal via an oxygen atom(s) lies within the aforementionedrange, and excellent transparency of the organic/inorganic composite isassured because the particle size is relatively small in comparison withthe wavelength of light passing through the organic/inorganic compositecontaining a rare earth metal or/and Period IV transition metal.

The light control optical element of the present invention may have astructure wherein the ratio of rare earth metal or/and Period IVtransition metal when mathematically converted to solid content is 90mass % or less of the total mass of the organic polymer and theinorganic dispersion phase wherein another metal is coordinated to theaforementioned rare earth metal or/and Period IV transition metal via anoxygen atom(s).

In accordance with the above structure, a high level of opticaltransmission can be expressed in fields involving optical functionapplications with which the present invention is closely related withoutbringing about scattering loss of light due to secondary aggregation ofthe rare earth metal that is coordinated to another metal via an oxygenatom(s).

In the light control optical element of the present invention, the metalcoordinated to the rare earth metal or/and Period IV transition metalvia an oxygen atom(s) is preferably one or more than one elementselected from a group consisting of Group 3B, Group 4A, and Group 5Ametals.

In accordance with the above structure, coordination of the other metalwith the rare earth metal via an oxygen atom(s) will be facilitated, andeffective dispersion into the organic polymer can thus be realizedthereby.

The light control optical element of the present invention may have astructure wherein the inorganic dispersion phase wherein a rare earthmetal or/and Period IV transition metal is coordinated to another metalvia an oxygen atom(s) is preferably formed by a rare earth metal saltand an alkoxide of the other metal.

In accordance with the above structure, the dispersion phase wherein theother metal coordinates with the rare earth metal or/and Period IVtransition metal via an oxygen atom(s) can be formed efficiently.

The organic/inorganic composite containing a rare earth metal or/and aPeriod IV transition metal used in the light control optical element ofthe present invention has a structure comprising a dispersion phasecontaining a rare earth metal or/and Period IV transition metal whereinanother metal is coordinated thereto via an oxygen atom(s); and anorganic polymer.

As a result, the present invention accomplishes the effect of providinga light control optical element wherein: a rare earth metal is doped ata high concentration; and assurances of optical transparency and oftransmission and absorption control of light a specific wavelength orwaveband are achieved without inducing degradation of the polymericmatrix material accompanied by energy transfer of absorbed UV light andmolecular chain cleavage.

8. A luminescent device having a light emitting element and anorganic/inorganic composite in which a rare earth metal luminescencematerial emitting light when excited by light generated by the lightemitting element is dispersed in an organic polymer, theorganic/inorganic composite being the organic/inorganic compositeaccording to item 1.

In accordance with the above structure, high concentration doping of therare earth metal luminescence material in the organic polymer can beachieved by coordinating another metal with the rare earth metal via anoxygen atom(s). In addition, because the other metal is coordinated viaan oxygen atom(s), quenching due to energy transfer between the rareearth metal and the CH and OH groups of the organic polymer isinhibited. Concurrently, quenching that accompanies proximityinteractions or/and cluster formation between the metal coordinated viaan oxygen atom(s) and the rare earth metal is also inhibited thereby.

Applications of coordination compounds intended for the dispersion of arare earth metal in an organic polymer are also described in theaforementioned prior art, and in general prior art coordination with anorganic compound is performed via an oxygen or nitrogen atom capable ofcoordination with a metal. However, the quenching due to energy transferbetween the rare earth metal and the CH and OH groups of the organicpolymer noted above cannot be inhibited by coordination wherein anorganic compound is used as a ligand.

If coordination with the other metal via an oxygen atom(s) is notperformed, aggregation will occur among the atoms of the rare earthmetal, and essentially dispersion in the organic polymer cannot occur.Even if dispersion at dilute concentrations were possible, it would beimpossible to form an organic/inorganic composite containing theintended rare earth metal due to quenching that accompanies proximityinteractions or/and cluster formation among the atoms of the rare earthmetal.

When used as an optical material and the like, it is desirable that theorganic polymer of the luminescent device of the present invention haveoptical transparency (permeability). The transmittance value of theorganic polymer is not particularly limited provided it is within arange having transparency, but a transmittance value of 30% to 100% ispreferable, and a range of 80% to 100% is even more preferable.

The luminescent device of the present invention may have a structurewherein the light emitting element comprises a semiconductor wherein themain ingredients are a Group III element and Group V element of thePeriodic Table, or a compound wherein the main ingredients are a GroupII element and a Group IV element of the Periodic Table.

In accordance with the above structure, not only light having awavelength in the visible bands, but also light of various wavelengthssuch as UV light and infrared light can be obtained. More specificallythe conversion efficiency from electric energy to light energy of theaforementioned semiconductor is much higher than with an incandescentbulb or discharge tubes, and it is optimal for constructing aluminescent device featuring low power consumption and high intensity.

The luminescent device of the present invention may have a structurewherein the particle size of the inorganic dispersion phase as a wholewherein another metal is coordinated to the aforementioned rare earthmetal via an oxygen atom(s) ranges from 0.1 to 1000 nm.

In accordance with the above structure, the average particle size of therare earth metal dispersion phase wherein another metal is coordinatedto the aforementioned rare earth metal via an oxygen atom(s) lies withinthe aforementioned range, and excellent transparency of theorganic/inorganic composite is assured because the particle size isrelatively small in comparison with the wavelengths of light passingthrough the organic/inorganic composite containing a rare earth metal.

The luminescent device of the present invention may have a structurewherein the ratio of rare earth metal when mathematically converted tosolid content is 90 mass % or less of the total mass of the organicpolymer and the inorganic dispersion phase wherein another metal iscoordinated to the rare earth metal via an oxygen atom(s).

In accordance with the above structure, a high level of opticaltransmission can be expressed in fields involving optical functionapplications with which the present invention is closely related withoutbringing about scattering loss of light due to secondary aggregation ofthe rare earth metal that is coordinated to another metal via an oxygenatom(s). Thus, if the ratio of rare earth metal when mathematicallyconverted to solid content is 90 mass % or less of the total mass of theorganic polymer and the inorganic dispersion phase wherein another metalis coordinated thereto via an oxygen atom(s), the object of the presentinvention can be attained thereby, and because the need will arise tocontrol absorption of the wavelength of light passing through theorganic/inorganic composite containing a rare earth metal in accordancewith the use of the organic/inorganic composite obtained in the presentinvention, the ratio of rare earth metal when mathematically convertedto solid content is preferably 30 mass % or less of the total mass ofthe organic polymer and the inorganic dispersion phase wherein anothermetal is coordinated to the aforementioned rare earth metal via anoxygen atom(s).

The luminescent device of the present invention may have a structurewherein the metal coordinated to the rare earth metal via an oxygenatom(s) is one or more than one element selected from a group consistingof Group 3B, Group 4A, and Group 5A metals.

In accordance with the above structure, coordination between the rareearth metal with another metal via an oxygen atom(s) will befacilitated, and effective dispersion into the organic polymer andeffective suppression of quenching during the light emission process ofthe rare earth metal can be realized thereby.

The luminescent device of the present invention may have a structurewherein the inorganic dispersion phase wherein a rare earth metal iscoordinated to another metal via an oxygen atom(s) is formed by a rareearth metal salt and an alkoxide of the other metal.

In accordance with the above structure, a dispersion phase whereinanother metal is coordinated to a rare earth metal is formedefficiently.

As noted above, the luminescent device of the present invention has astructure comprising: a light emitting element that converts electricenergy to light energy; a rare earth metal luminescence materialcomprising an inorganic dispersion phase containing a rare earth metalwherein another metal is coordinated thereto via an oxygen atom(s); andan organic polymer.

As a result, the present invention: (1) enables high concentrationdoping of a rare earth metal (2) suppresses quenching and (3) can assureoptical transparency. In addition, because the present invention doesnot require expensive starting materials such as fluorides anddeuterides to suppress quenching and a high temperature process to forma host material such as oxide crystals and the like, it provides theeffect of (4) realizing a assurance of cost effectiveness. In otherwords, an effect is realized in which a luminescent device is providedwherein a rare earth metal luminescence material is doped at a highconcentration, suppression of quenching and optical transparency areassured, and cost effectiveness is excellent.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic drawing of the inorganic dispersion phase whereinanother metal is coordinated to a rare earth metal/and Period IVtransition metal via an oxygen atom(s) among the organic/inorganiccomposites of the present invention;

FIG. 2 is a diagram showing the photoluminescence spectrum of theorganic/inorganic composite containing erbium used in Example 1 amongthe inorganic/organic composites of the present invention;

FIG. 3 is a spectrogram showing the absorption spectrum of theorganic/inorganic composite containing neodymium used in Example 2 amongthe organic/inorganic composites containing a rare earth metal or/andPeriod IV transition metal of the present invention;

FIG. 4 is a graph showing the photoluminescence spectrum of thewavelength specific to the composite nanoparticles containingNdAl/photopolymerized acrylic resin composite prepared according to theabove method;

FIG. 5 is a graph showing the photoluminescence spectrum of thewavelength specific to the composite nanoparticles containingEuAl/photopolymerized acrylic resin composite;

FIG. 6 is a graph showing the photoluminescence spectrum of thewavelength specific to the composite nanoparticles containingTbAl/photopolymerized acrylic resin composite prepared according to theabove method;

FIG. 7 is a graph showing the photoluminescence spectrum of thewavelength specific to the composite nanoparticles containingTbTi/photopolymerized acrylic resin composite prepared according to theabove method;

FIG. 8 is a graph showing the photoluminescence spectrum of thewavelength specific to the composite nanoparticles containingCeAl/photopolymerized acrylic resin composite;

FIG. 9 is an absorption spectrogram of the organic/inorganic compositecontaining Pr—Al used in Example 10 among the organic/inorganiccomposites of the present invention;

FIG. 10 is an absorption spectrum of the organic/inorganic compositecontaining Ni used in Example 11 among the organic/inorganic compositesof the present invention;

FIG. 11( a) is a schematic diagram showing the basic structure of anoptical amplifier that is an optical fiber amplifier;

FIG. 11( b) is a schematic drawing showing the basic structure of anoptical amplifier that is an optical waveguide amplifier;

FIG. 12 is an optics diagram measuring the optical amplificationproperties using an optical waveguide amplifier comprising the Er—Alorganic/inorganic composite prepared in Example 12 among the opticalamplifiers of the present invention;

FIG. 13( a) is a drawing showing a typical light control optical elementof the present invention;

FIG. 13( b) is a drawing showing a typical light control optical elementof the present invention;

FIG. 13( c) is a drawing showing a typical light control optical elementof the present invention;

FIG. 13( d) is a drawing showing a typical light control optical elementof the present invention;

FIG. 14( a) is a schematic drawing of a electric bulb as an example of aluminescent device;

FIG. 14( b) is a schematic drawing of a discharge tube as an example ofa luminescent device;

FIG. 14( c) is a schematic drawing of an LED as an example of aluminescent device;

FIG. 15 is a photoluminescence spectrum in accordance with the mixedemission from the Eu—Al fluorescent material, the Tb—Al fluorescentmaterial, and the Ce—Al fluorescent material used in Example 4 among theluminescent devices of the present invention; and

FIG. 16 is a chromaticity diagram concerning the mixed emission from theEu—Al fluorescent material, the Tb—Al fluorescent material and the Ce—Alfluorescent material used in Example 4 among the luminescent devices ofthe present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention is explained in greater detail below.

The organic/inorganic composite of the present invention is a compositeof a rare earth metal/and a Period IV transition metal and an organicpolymer to be used in fields involving optical function applicationswherein the transmission, refraction, reflection, polarization planerotation, and the like of incident light are controlled, and functionssuch as luminescence (fluorescence) due to excitation by incident light,amplification, and the like are expressed, said organic/inorganiccomposite comprising an inorganic dispersion phase (rare earth metal/andPeriod IV transition metal dispersion phase) wherein another metalcoordinates thereto via an oxygen atom(s); and an organic polymer. Inaddition, the organic/inorganic composite of the present invention is acomposite wherein at least one species of rare earth metal is dispersedin the organic polymer, and it may be an organic/inorganic compositecontaining a rare earth metal wherein another metal coordinates theretovia an oxygen atom(s).

The structure of the organic/inorganic composite of the presentinvention may be any combination of the following provided it contains arare earth metal or/and Period IV transition metal; a metal capable ofcoordinating with the rare earth metal or/and Period IV transition metalvia an oxygen atom(s); and an organic polymer. The method of forming theinorganic dispersion phase wherein another metal coordinates with therare earth metal or/and Period IV transition metal via an oxygen atom(s)is not particularly limited, and it may be formed, for example, by areaction between a rare earth metal salt/and Period IV transition metalsalt and a metal alkoxide. The composite containing the inorganicdispersion phase wherein the rare earth metal/and Period IV transitionmetal is coordinated to another metal via an oxygen atom(s) can beprepared, for example, by mixing and dispersing an inorganic dispersionphase formed by a reaction between the aforementioned metal alkoxide andthe rare earth metal salt/and Period IV transition metal salt togetherwith an organic polymer.

[Rare Earth Metal] All of the following may be used as the rare earthmetal: scandium, yttrium, lanthanum, cerium, praseodymium, neodymium,promethium, samarium, europium, gadolinium, terbium, dysprosium,holmium, erbium, thulium, ytterbium, and lutetium.

[Period IV Transition Metal] Vanadium, chromium, manganese, iron,cobalt, nickel, and copper are preferably used as the Period IVtransition metal. A composite may be formed containing only one species,or two or more species of the rare earth metal and Period IV transitionmetal.[Other Metal Coordinating with the Rare Earth Metal/and Period IVTransition Metal Via an Oxygen Atom(s)] The other metal is notparticularly limited provided it is an element that can coordinate witha rare earth metal via an oxygen atom(s) and does not have an adverseeffect on the required properties. Preferably, metals from Group 3B,Group 4A or Group 5A are used. More preferably, aluminum, gallium,titanium, zirconium, niobium, and tantalum are used.[Preparation of Inorganic Dispersion Phase] The method of forming theinorganic dispersion phase is not particularly limited providedcoordination bonding of the other metal with the intended rare earthspecies via an oxygen atom(s) is possible. The following methods, forexample, are available: methods involving heat treatment andpulverization (when a metal salt, hydroxide, oxide, and the like is usedas the starting material) after mixing the rare earth metal or/andPeriod IV transition metal starting material and the starting materialof the metal capable of coordinating thereto; methods wherein the rareearth metal or/and Period IV transition metal and the metal capable ofcoordinating thereto are dissolved in a solvent, and then precipitatedby hydrolysis; and methods wherein a rare earth metal salt/and Period IVtransition metal salt is reacted with the alkoxide of the metal capableof coordinating thereto in an organic solvent.

To obtain a nanometer sized rare earth metal/and Period IV transitionmetal dispersion phase, the method wherein a rare earth metal salt/andPeriod IV transition metal salt is reacted with the alkoxide of a metalcapable of coordinating thereto in an organic solvent is preferablyused. The solvent to be used is not particularly limited, and anysolvent may be used provided the ultimate reaction product that formsthe coordination structure can be dispersed in the organic polymer. Forexample, a primary alcohol such as methanol, ethanol, 1-propanol,2-propanol, 1-butanol, 2-butanol, t-butanol and the like; a polyhydricalcohol such as ethylene glycol, propylene glycol, glycerin, and thelike; a glycol ether such as ethylene glycol monomethyl ether, ethyleneglycol monoethyl ether, ethylene glycol monopropyl ether, propyleneglycol-α-monomethyl ether, propylene glycol-α-monoethyl ether, and thelike; a ketone such as acetone, methyl ethyl ketone, and the like; acyclic ether such as tetrahydrofuran, dioxane, and the lie; an estersuch as methyl acetate, ethyl acetate, propyl acetate and the like;acetonitrile; an aromatic compound such as benzene, toluene, xylene, andthe like; and a hydrocarbon such as pentane, hexane, heptane,cyclohexane, and the like can be used as such a solvent. It is possibleto use a method wherein heating to the reflux temperature of the solventis performed to form the coordination compound, and this method is aneffective means because in many cases the reaction speed is acceleratedthereby. It is possible to control the size of the inorganic dispersionby adding water to the coordination product obtained thereby andperforming hydrolysis.

An organic acid salt such as a formate, acetate, oxalate, and the likeof a mineral acid such as nitric acid, sulfuric acid, carbolic acid, andhydrochloric acid, or an alkoxide and the like thereof is used as thestarting material for the rare earth metal or/and Period IV transitionmetal. In consideration of reducing anionic impurities and the like, theuse of an organic acid salt such as a formate, acetate, oxalate and thelike and an alkoxide is preferred. The use of acetate is even morepreferred. The acetate of a rare earth metal/and Period IV transitionmetal normally contains water of crystallization, and can be usedunchanged depending on the type of metal to be coordinated, but beforethe reaction it is preferable to perform a dehydration treatment.

The functional group R of the dispersion phase shown in FIG. 1 is notparticularly limited, and is selected depending on the type of organicpolymer forming the composite. To increase the miscibility with theorganic polymer, it is possible to make the selection with the purposeof imparting properties to make it polymerizable with the organicpolymer or the monomer ingredients that can form the organic polymer.For example, R can be a hydrogen, alkyl group, reactive vinyl group,aryl group, diazo group, nitro group, cinnamoyl group, acryloyl group,imide group, epoxy group, cyano group, or an alkyl group, alkyl silylgroup, alkyl carbonyl group and the like containing these functionalgroups.

In addition, provided it can form a uniform composite with the polymerforming the composite, an organic polymer having a functional groupcontaining an active hydrogen such as a carboxylate group such as poly(meth)acrylic acid, polyethylene glycol, polyethylene oxide, celluloseand the like, a hydroxyl group, an amino group, an amide group, and thelike can be used.

The following methods can be used for introducing the functional group Rinto the inorganic dispersion phase: (1) a method wherein insertion isperformed by a reaction after the inorganic dispersion phase has beenformed; and (2) a method wherein the R group is inserted beforehand intoan alkoxide as the starting material that can coordinate with the rareearth metal or/and Period IV transition metal, and then a rare earthmetal salt or/and Period IV transition metal salt is reacted thereto.

The compound to be reacted with the inorganic dispersion phase is notparticularly limited provided it can form the aforementioned intendedstructure, and the following are preferably used: For method (1), acompound having a terminal active hydrogen such as a carboxylate group,hydroxyl group, amino group, amide group, and the like; and for method(2) a compound that can react with the inorganic dispersion phase bycondensation such as an alkoxysilane containing an alkyl group, reactivevinyl group, aryl group, diazo group, nitro group cinnamoyl group,acryloyl group, imide group, epoxy group, cyano group, or an alkyl groupcontaining these functional groups (R1R2R3SiOR4, wherein R1 is an alkylgroup, reactive vinyl group, aryl group, diazo group, nitro group,cinnamoyl group, acryloyl group, imide group, epoxy group, cyano group,or an alkyl group containing these functional groups, R2 and R3 eachrepresents a hydrogen atom, alkyl group, reactive vinyl group, arylgroup, diazo group, nitro group, cinnamoyl group, acryloyl group, imidegroup, epoxy group, cyano group, or an alkyl or alkoxyl group containingthese functional groups, and R4 is an alkyl group); an alkoxygermane(R1R2R3GeOR4, wherein R1 is an alkyl group, reactive vinyl group, arylgroup, diazo group, nitro group, cinnamoyl group, acryloyl group, imidegroup, epoxy group, cyano group, or an alkyl group containing thesefunctional groups, R2 and R3 each represents a hydrogen atom, alkylgroup, reactive vinyl group, aryl group, diazo group, nitro group,cinnamoyl group, acryloyl group, imide group, epoxy group, cyano group,or an alkyl or alkoxyl group containing these functional groups, and R4is an alkyl group) and the like.

[Organic Polymer] The organic polymer is not particularly limitedprovided dispersion is possible without aggregation of the rare earthmetal/and Period IV transition metal wherein another metal iscoordinated thereto, but preferably an organic polymer is used that hassubstantial transparency in the waveband region wherein the expressionof optical function is to be utilized. The waveband region wherein theexpression of optical function is to be utilized is not particularlylimited to violet-red visible bands, and regions of UV light and x-rayswith a wavelength shorter than the approximately 400 nm wavelength ofviolet, and infrared light with a wavelength longer than theapproximately 750 nm wavelength of red light can also be used. Thefollowing can be listed as examples of the organic polymer, but theorganic polymer of the present invention is by no means limited thereto:polymethyl methacrylate, polycyclohexyl methacrylate, polybenzylmethacrylate, polyphenyl methacrylate, polycarbonate, polyethyleneterephthalate, polystyrene, polytetrafluoroethylene,poly-4-methylpentene-1, polyvinyl alcohol, polyethylene,polyacrylonitrile, styrene-acrylonitrile copolymer, polyvinyl chloride,polyvinyl carbazole, styrene-maleic anhydride copolymer, polyolefin,polyimide, epoxy resin, polysiloxane, polysilane, polyamide, cyclicolefin resin, and the like. The organic polymer can be used alone, or acombination of two or more organic polymers can be used.

The organic polymer can be worked into the form of the intendedorganic/inorganic composite containing a rare earth metal/and Period IVtransition metal by dissolving the same in a solvent or by melting it byheating and the like, and it is possible to polymerize the organicpolymer in the process of working it into the form of the intendedorganic/inorganic composite by using a mixture of an organic polymerprecursor such as a monomer, an oligomer, or a monomer and oligomer, andthe organic polymer.

In addition, these organic polymers may have functional groups thatpromote an addition, crosslinking, polymerization, or other type ofreaction initiated by light and heat on the main chain or side chainthereof. Examples of such a functional group include a hydroxyl group,carbonyl group, carboxyl group, diazo group, nitro group, cinnamoylgroup, acryloyl group, imide group, epoxy group, and the like.

The organic polymer may include an additive such as a stabilizer such asa plasticizer, antioxidant, and the like, a surfactant, a solubilizationpromoter, polymerization inhibitor, and a colorant such as a dye,pigment, and the like. In addition, the organic polymer may include asolvent (water, alcohol, glycol, Cellosolve, ketone, ester, ether,amide, or organic solvent such as a hydrocarbon and the like) to enhancemolding properties such as coating performance and the like.

The present invention is described in greater detail below throughexamples, but the present invention is by no means limited to theseexamples.

EXAMPLE 1 Preparation of Inorganic Dispersion Phase

Erbium acetate that had been dehydrated for 1 hour at 110° C. andtri-s-butoxy aluminum were added together in 2-butanol (Er/Al=3 molar,mathematically converted concentration of total oxides of Er and Al 5mass %) and refluxed for 1 hour to obtain a light pink transparentliquid. The particle size of the reaction product obtained thereby wasmeasured using dynamic light scattering, and it was confirmed that thereaction product comprised composite nanoparticles with a peak top of1.7 nm in diameter. In addition, coordination of the Al via an oxygenatom(s) with the Er was verified before and after the reaction withtri-s-butoxy aluminum by the change in 27Al-NMR spectrum.

<Preparation of Composite of Inorganic Dispersion Phase and TransparentOrganic Polymer>

A photopolymerizable acrylic resin “Cyclomer” (Daicel ChemicalIndustries, Ltd.) was used as the transparent organic polymer. Thisorganic polymer, the composite nanoparticles containing ErAl preparedaccording to the above method, and a photoradical initiator “Irgacure369” (Ciba Specialty Chemicals) were mixed together in PGMEA, andstirred for 2 hours at room temperature to obtain a liquid mixture. Themixture ratio was controlled so that the Er contents are 5.2% and 0.52%in mass in terms of solid content of the composite.

After bonding a frame of polytetrafluoroethylene plates to a fusedquartz plate as a mold, the liquid mixture formulated as noted above waspoured into the interior of the polytetrafluoroethylene mold, and anapproximately 1 mm thick cast molded product of the organic/inorganiccomposite containing a rare earth metal was obtained by evaporating thePGMEA at 100° C. and drying. The transmittance value of the moldedproduct obtained thereby was 93% at a wavelength of 633 nm, which wasequivalent to the transmittance value of the organic polymer not dopedby the rare earth metal, and it was confirmed that optical transparencycan be assured.

<Measurement of Photoluminescence Intensity>

The organic/inorganic composite containing Er obtained in the abovemanner was irradiated with an argon laser at a wavelength of 514 nm, andthe Photoluminescence intensity was measured. FIG. 2 is a graph of thefluorescence spectrum of the wavelengths of the composite nanoparticlescontaining Er—Al/photopolymerizable acrylic resin composite prepared inthe above manner. In the drawing, (a) represents the fluorescencespectrum of a test sample containing an erbium (Er) concentration of5.2%, and likewise (b) represents the fluorescence spectrum of a testsample containing a erbium concentration of 0.52%. As a result, as shownin FIG. 2, the fluorescence specific to erbium was observed in thevicinity of a wavelength of 1550 nm. Based on these results, it wasconfirmed that even when doped with a high concentration of the rareearth metal, quenching is controlled and the emission process of Er canbe expressed thereby.

EXAMPLE 2 Preparation of the Inorganic Dispersion Phase

Neodymium acetate that had been dehydrated under vacuum for 1 hour at110° C. and tri-s-butoxy aluminum were added together in propyleneglycol α-monomethyl ether (Nd/Al=3 molar, mathematically convertedconcentration of total oxides of Er and Al 5 mass %) and refluxed for 1hour to obtain a light purple transparent liquid. The particle size ofthe reaction product obtained thereby was measured using dynamic lightscattering, and it was confirmed that the reaction product comprisedcomposite nanoparticles with a peak top of 2.3 nm in diameter. Inaddition, coordination of the Al via an oxygen atom(s) with the Nd wasverified before and after the reaction with tri-s-butoxy aluminum by thechange in 27Al-NMR spectrum.

<Preparation of Composite of Inorganic Dispersion Phase and TransparentOrganic Polymer>

Hydroxypropyl cellulose (Nippon Soda Co., Ltd.) was used as thetransparent organic polymer. This organic polymer and the compositenanoparticles containing NdAl prepared according to the above methodwere mixed together in Ethyl Cellosolve, and stirred for 2 hours at roomtemperature to obtain a liquid mixture. The mixture ratio was controlledso that the neodymium (Nd) content is 8% in mass in terms of solidcontent of the composite.

The liquid mixture formulated as noted above was poured into apolytetrafluoroethylene container used as mold, and an approximately 1mm thick cast molded product of the organic/inorganic compositecontaining Nd was obtained by evaporating the Ethyl Cellosolve at 120°C. and drying.

<Measurement of Spectroscopic Absorption Properties>

The spectroscopic absorption properties of the organic/inorganiccomposite containing Nd obtained thereby was measured using aspectrophotometer. FIG. 3 shows the spectroscopic absorption spectrum ofthe composite nanoparticles containing Nd—Al/hydroxypropyl cellulosecomposite prepared according to the above method. It is clear thatabsorption in the wavebands of approximately 500 to 540 nm andapproximately 560 to 600 nm originating from the Nd absorption can beassured in the composite nanoparticles containing Nd—Al/hydroxypropylcellulose composite.

<Measurement of Photoluminescence Intensity>

The organic/inorganic composite containing Nd obtained in the abovemanner was irradiated with an argon laser at a wavelength of 514 nm, andthe Photoluminescence intensity was measured. FIG. 4 is a graph of thefluorescence spectrum of the wavelengths of the composite nanoparticlescontaining Nd—Al/photopolymerizable acrylic resin composite prepared inthe above manner. As a result, as shown in FIG. 4, the fluorescencespecific to neodymium (Nd) was observed in the vicinity of a wavelengthof 1075 nm. Based on these results, it was confirmed that even whendoped with a high concentration of the rare earth metal, quenching issuppressed and the emission process of neodymium can be expressedthereby.

EXAMPLE 3 Preparation of the Inorganic Dispersion Phase

Neodymium acetate that had been dehydrated under vacuum for 1 hour at110° C. and tri-s-butoxy aluminum were added together in propyleneglycol α-monomethyl ether (Eu/Al=3 molar, mathematically convertedconcentration of total oxides of Eu and Al 5 mass %) and refluxed for 1hour to obtain a colorless transparent liquid. The particle size of thereaction product obtained thereby was measured using dynamic lightscattering, and it was confirmed that the reaction product comprisedcomposite nanoparticles with a peak top of 1.5 nm in diameter. Inaddition, coordination of the Al via an oxygen atom(s) with the Eu wasverified before and after the reaction with tri-s-butoxy aluminum by thechange in 27Al-NMR spectrum.

<Preparation of Composite of Inorganic Dispersion Phase and TransparentOrganic Polymer>

Hydroxypropyl cellulose (Nippon Soda Co., Ltd.) was used as thetransparent organic polymer. This organic polymer and the compositenanoparticles containing Eu—Al prepared according to the above methodwere mixed together in Ethyl Cellosolve, and stirred for 2 hours at roomtemperature to obtain a liquid mixture. The mixture ration wascontrolled so that the europium (Eu) content is 8% in mass in terms ofsolid content of the composite.

The liquid mixture formulated as noted above was poured into apolytetrafluoroethylene container used as mold, and an approximately 1mm thick cast molded product of the organic/inorganic compositecontaining Eu was obtained by evaporating the Ethyl Cellosolve at 120°C. and drying.

<Measurement of Photoluminescence Intensity>

The organic/inorganic composite containing Eu obtained in the abovemanner was irradiated with a xenon laser at a wavelength of 380 nmextracted by a filter, and the Photoluminescence intensity was measured.FIG. 5 is a graph of the fluorescence spectrum of the wavelengths of thecomposite nanoparticles containing EuAl/photopolymerizable acrylic resincomposite prepared in the above manner. As a result, as shown in FIG. 5,the fluorescence specific to europium was observed in the vicinity of awavelength of 615 nm.

EXAMPLE 4 Preparation of Composite of Inorganic Dispersion Phase andTransparent Organic Polymer

An amount of methacrylic acid equivalent to double the molar amount ofAl was added to the composite nanoparticles containing Eu—Al prepared inExample 3, and after the mixture was stirred for 2 hours at roomtemperature, the solvent was removed under vacuum at 40° C. or lower toobtain a colorless transparent syrup-like residue. After methylmethacrylate was added to the colorless transparent residue toreconstitute a transparent liquid, pentaerythritol tetraacrylate andIrgacure 149 were added (methyl methacrylate/pentaerythritoltetraacetate: mass ratio 90/10, Irgacure 149=1.5% with respect toacrylic monomer), and a solid, transparent organic/inorganic compositecontaining 5 mass % Eu was obtained by irradiating the mixture in a 5 mmdiameter glass container with a high pressure mercury vapor lamp. Thered luminescence characteristic of Eu was observed by irradiating theorganic/inorganic containing Eu obtained thereby with a UV-emitting LEDat a wavelength of 395 nm.

EXAMPLE 5 Preparation of Inorganic Dispersion Phase

Terbium acetate that had been dehydrated under vacuum for 1 hour at 110°C. and tri-s-butoxy aluminum were added together in propylene glycolα-monomethyl ether (Tb/Al=3 molar, mathematically convertedconcentration of total oxides of Tb and Al 5 mass %) and refluxed for 1hour to obtain a colorless transparent liquid. The particle size of thereaction product obtained thereby was measured using dynamic lightscattering, and it was confirmed that the reaction product comprisedcomposite nanoparticles with a peak top of 2.3 nm in diameter. Inaddition, coordination of the Al via an oxygen atom(s) with the Tb wasverified before and after the reaction with tri-s-butoxy aluminum by thechange in 27Al-NMR spectrum.

<Preparation of Composite of Inorganic Dispersion Phase and TransparentOrganic Polymer>

Hydroxypropyl cellulose (Nippon Soda Co., Ltd.) was used as thetransparent organic polymer. This organic polymer and the compositenanoparticles containing Tb—Al prepared according to the above methodwere mixed together in Ethyl Cellosolve, and stirred for 2 hours at roomtemperature to obtain a liquid mixture. The mixture ratio was controlledso that the Tb content is 8% in mass in terms of solid content of thecomposite.

The liquid mixture formulated as noted above was poured into apolytetrafluoroethylene container used as mold, and an approximately 1mm thick cast molded product of the organic/inorganic compositecontaining Tb was obtained by evaporating the Ethyl Cellosolve at 120°C. and drying.

<Measurement of Photoluminescence Intensity>

The organic/inorganic composite containing Tb obtained in the abovemanner was irradiated with a xenon laser at a wavelength of 380 nmextracted by a filter, and the Photoluminescence intensity was measured.FIG. 6 is a graph of the fluorescence spectrum of the wavelengths of thecomposite nanoparticles containing Tb—Al/photopolymerizable acrylicresin composite prepared in the above manner. As a result, as shown inFIG. 6, the fluorescence specific to terbium (Tb) was observed in thevicinity of a wavelength of 540 nm.

EXAMPLE 6 Preparation of the Inorganic Dispersion Phase

Terbium acetate that had been dehydrated under vacuum for 1 hour at 110°C. and tetraisopropyl titanium were added together in propylene glycolα-monomethyl ether (Tb/Ti=3 molar, mathematically convertedconcentration of total oxides of Tb and Ti 5 mass %) and refluxed for 1hour to obtain a colorless transparent liquid. The particle size of thereaction product obtained thereby was measured using dynamic lightscattering, and it was confirmed that the reaction product comprisedcomposite nanoparticles with a peak top of 1.0 nm in diameter.

<Preparation of Composite of Inorganic Dispersion Phase and TransparentOrganic Polymer>

Hydroxypropyl cellulose (Nippon Soda Co., Ltd.) was used as thetransparent organic polymer. This organic polymer and the compositenanoparticles containing TbTi prepared according to the above methodwere mixed together in Ethyl Cellosolve, and stirred for 2 hours at roomtemperature to obtain a liquid mixture. The mixture ratio was controlledso that the Tb content is 8% in mass in terms of solid content of thecomposite.

The liquid mixture formulated as noted above was poured into apolytetrafluoroethylene container used as mold, and an approximately 1mm thick cast molded product of the organic/inorganic compositecontaining Tb was obtained by evaporating the Ethyl Cellosolve at 120°C. and drying.

<Measurement of Photoluminescence Intensity>

The organic/inorganic composite containing Tb obtained in the abovemanner was irradiated with a xenon laser at a wavelength of 380 nmextracted by a filter, and the Photoluminescence intensity was measured.FIG. 7 is a graph of the fluorescence spectrum of the wavelengths of thecomposite nanoparticles containing Tb—Ti/photopolymerizable acrylicresin composite prepared in the above manner. As a result, as shown inFIG. 7, a broad emission with a peak wavelength near 465 nm was observedin addition to the fluorescence specific to terbium (Tb) that wasobserved in the vicinity of a wavelength of 540 nm. As a result, when wecompare the results obtained in Example 5 and those in Example 6, it isclear that emission properties can be controlled by changing the metalcoordinating with Tb via an oxygen atom(s) from Al to Ti.

EXAMPLE 7 Preparation of Composite of Inorganic Dispersion Phase andTransparent Organic Polymer

An amount of methacrylic acid equivalent to double the molar amount ofAl was added to the composite nanoparticles containing Tb—Al prepared inExample 5, and after the mixture was stirred for 2 hours at roomtemperature, the solvent was removed under vacuum at 40° C. or lower toobtain a colorless transparent syrup-like residue. After methylmethacrylate was added to the colorless transparent residue toreconstitute a transparent liquid, pentaerythritol tetraacrylate andIrgacure 149 were added (methyl methacrylate/pentaerythritoltetraacetate: mass ratio 90/10, Irgacure 149=1.5% with respect toacrylic monomer), and a solid, transparent organic/inorganic compositecontaining 5 mass % Tb was obtained by irradiating the mixture in a 5 mmdiameter glass container with a high pressure mercury vapor lamp. Thegreen luminescence characteristic of Tb was observed by irradiating theorganic/inorganic containing Tb obtained thereby with a UV-emitting LEDat a wavelength of 395 nm.

EXAMPLE 8 Preparation of the Inorganic Dispersion Phase

Cerium acetate that had been dehydrated under vacuum for 1 hour at 110°C. was added to propylene glycol α-monomethyl ether and heat-treated at100° C. for 24 hours. Then tri-s-butoxy aluminum was added (Ce/Al=3molar, mathematically converted concentration of total oxides of Ce andAl 5 mass %) and the mixture was refluxed for 1 hour to obtain a paleyellow transparent liquid.

<Preparation of Composite of Inorganic Dispersion Phase and TransparentOrganic Polymer>

Hydroxypropyl cellulose (Nippon Soda Co., Ltd.) was used as thetransparent organic polymer. This organic polymer and the compositenanoparticles containing Ce—Al prepared according to the above methodwere mixed together in Ethyl Cellosolve, and stirred for 2 hours at roomtemperature to obtain a liquid mixture. The mixture ratio was controlledso that the Ce content is 8% in mass in terms of solid content of thecomposite.

The liquid mixture formulated as noted above was poured into apolytetrafluoroethylene container used as mold, and an approximately 1mm thick cast molded product of the organic/inorganic compositecontaining Ce was obtained by evaporating the Ethyl Cellosolve at 120°C. and drying.

<Measurement of Photoluminescence Intensity>

The organic/inorganic composite containing Ce obtained in the abovemanner was irradiated with a xenon laser at a wavelength of 380 nmextracted by a filter, and the Photoluminescence intensity was measured.FIG. 7 is a graph of the fluorescence spectrum of the wavelengths of thecomposite nanoparticles containing Ce—Al/photopolymerizable acrylicresin composite prepared in the above manner. As a result, as shown inFIG. 8, the fluorescence specific to cerium (Ce) that was observed inthe vicinity of a wavelength range of 400 to 500 nm.

EXAMPLE 9 Preparation of Composite of Inorganic Dispersion Phase andTransparent Organic Polymer

An amount of methacrylic acid equivalent to double the molar amount ofAl was added to the composite nanoparticles containing Ce—Al prepared inExample 8, and after the mixture was stirred for 2 hours at roomtemperature, the solvent was removed under vacuum at 40° C. or lower toobtain a colorless transparent syrup-like residue. After methylmethacrylate was added to the colorless transparent residue toreconstitute a transparent liquid, pentaerythritol tetraacrylate andIrgacure 149 were added (methyl methacrylate/pentaerythritoltetraacetate: mass ratio 90/10, Irgacure 149=1.5% with respect toacrylic monomer), and a solid, transparent organic/inorganic compositecontaining 5 mass % Ce was obtained by irradiating the mixture in a 5 mmdiameter glass container with a high pressure mercury vapor lamp. Theblue luminescence characteristic of Ce was observed by irradiating theorganic/inorganic containing Tb obtained thereby with a UV-emitting LEDat a wavelength of 395 nm.

EXAMPLE 10 Preparation of the Inorganic Dispersion Phase

Praseodymium acetate that had been dehydrated for 1 hour at 110° C. andtri-s-butoxy aluminum were added together in propyleneglycol-α-monomethyl ether (Pr/Al=3 molar, mathematically convertedconcentration of total oxides of Pr and Al 5 mass %) and refluxed for 1hour to obtain a light green transparent liquid. The particle size ofthe reaction product obtained thereby was measured using dynamic lightscattering, and it was confirmed that the reaction product comprisedcomposite nanoparticles with a peak top of 6.5 nm in diameter. Inaddition, coordination of the Al via an oxygen atom(s) with the Pr wasverified before and after the reaction with tri-s-butoxy aluminum by thechange in 27Al-NMR spectrum.

<Preparation of Composite of Inorganic Dispersion Phase and TransparentOrganic Polymer>

A photopolymerizable acrylic resin “Cyclomer” (Daicel ChemicalIndustries, Ltd.) was used as the transparent organic polymer. Thisorganic polymer, the composite nanoparticles containing PrAl preparedaccording to the above method, and a photoradical initiator “Irgacure369” (Ciba Specialty Chemicals) were mixed together in PGMEA, andstirred for 2 hours at room temperature to obtain a liquid mixture. Themixture ratio was controlled so that the praseodymium (Pr) content is10% in mass in terms of solid content of the composite.

Using a polytetrafluoroethylene container as a mold, an approximately 1mm thick transparent cast molded product of the organic/inorganiccomposite containing Pr was obtained by evaporating the PGMEA at 120° C.and drying.

<Measurement of Spectroscopic Absorption Properties>

The spectroscopic absorption properties of the organic/inorganiccomposite containing Pr obtained thereby was measured using aspectrophotometer. FIG. 9 shows the spectroscopic absorption spectrum ofthe composite nanoparticles containing PrAl/photopolymerizable acrylicresin composite prepared according to the above method. It is clear thatabsorption in the wavebands of approximately 440 to 490 nm originatingfrom the Pr absorption can be assured in the composite nanoparticlescontaining Ni—Nb/photopolymerizable acrylic resin composite.

EXAMPLE 11 Preparation of the Inorganic Dispersion Phase

Nickel acetate that had been dehydrated for 1 hour under vacuum at 100°C. and pentaethoxy niobium were added together in ethylene glycolmonomethyl ether (Ni/Nb=2 molar, mathematically converted concentrationof total oxides of Ni and Nb 5 mass %) and refluxed for 1 hour to obtaina green transparent liquid. The particle size of the reaction productobtained thereby was measured using dynamic light scattering, and it wasconfirmed that the reaction product comprised composite nanoparticleswith a peak top of 2.9 nm in diameter.

<Preparation of Composite of Inorganic Dispersion Phase and TransparentOrganic Polymer>

Hydroxypropyl cellulose (Nippon Soda Co., Ltd.) was used as thetransparent organic polymer. This organic polymer and the compositenanoparticles containing Ni—Nb prepared according to the above methodwere mixed together in Ethyl Cellosolve, and stirred for 2 hours at roomtemperature to obtain a liquid mixture. The mixture ratio was controlledso that the Ni content is 8% in mass in terms of solid content of thecomposite.

The liquid mixture formulated as noted above was poured into apolytetrafluoroethylene container used as mold, and an approximately 1mm thick transparent cast molded product of the organic/inorganiccomposite containing Ni was obtained by evaporating the Ethyl Cellosolveat 120° C. and drying.

<Measurement of Spectroscopic Transmittance Value>

The spectroscopic absorption properties of the organic/inorganiccomposite containing Ni obtained thereby was measured using aspectrophotometer. FIG. 10 shows the spectroscopic absorption spectrumof the composite nanoparticles containing the Ni—Nb/hydroxypropylcellulose composite prepared according to the above method. It is clearthat absorption in the wavebands of approximately 900 to 600 nm andapproximately 450 nm or less originating from the Ni absorption can beassured in the composite nanoparticles containing Ni—Nb/hydroxypropylcellulose composite.

Based on the above results the present invention makes it possible toprovide an organic/inorganic composite wherein a rare earth metal or/andPeriod IV transition metal is doped at a high concentration in anorganic polymer, and the original absorption properties of the dopingelements can be expressed thereby. In addition, by doping with a rareearth metal it can be assured that quenching, which has been impossibleto avoid with conventional, high concentration doping can be controlledand that the luminescent process specific to each doping element can beexpressed.

COMPARISON EXAMPLE

The solubility in organic solvents and dispersion properties in organicpolymers of the metal salts and oxides of various rare earth or/andPeriod IV transition metals were demonstrated, but it was not possibleto obtain transparent solutions and transparent dispersions.

The present invention relates to an organic/inorganic composite that isa composite of a rare earth metal or/and a period IV transition metaland an organic polymer to be used most suitably in fields involvingoptical function applications wherein the transmission, refraction,reflection, polarization plane rotation, and the like of incident lightare controlled, and functions such as luminescence (fluorescence) due toexcitation by incident light, amplification, and the like are expressed.Various optical functions can be expressed by selecting the rare earthmetal or/and Period IV transition metal salt, type of coordinating metalor organic polymer in accordance with the purpose and by forming theorganic/inorganic composite containing a rare earth metal or/and PeriodIV transition metal in accordance with the intended use. A high indexmaterial can be listed as such an example. In the past cerium,lanthanum, and the like have been used to make a glass lens highlyrefractive. The present invention can be utilized to make an organicpolymer material highly refractive because the rare earth metal thereincan be dispersed in the organic polymer at a high concentration.Materials for parts having a magneto-optical effect such asmagneto-optical recording disks and the like can be listed as anapplication of the present invention. In the past, gadolinium, terbium,and the like have been used for this application, but the disks havebeen formed by vacuum deposition, sputtering, and the like. The presentinvention can be applied to applied to a wide range of plastic bodiesfrom thin films to bulk compacts using inexpensive means such ascoating, casting, and the like because these rare earth metals can bedispersed within an organic polymer. Light control optical materials canalso be listed as an application of the present invention. In the pastcolored glass materials have been obtained wherein color rending iscontrolled by doping glass with a rare earth metal such as cerium,praseodymium, erbium, neodymium, and the like, and such materials havebeen used in electric lamps that enhance the coloring of food on atable, sunglasses, and the like. The present invention can be used toprepare optical resins wherein the color rendering is adjusted by dopingan organic polymer with the rare earth metals in accordance with thepresent invention. An optical amplifier can also be listed as anapplication of the present invention. In the past erbium, thulium,praseodymium, dysprosium, and the like have been doped into opticalfiber and used as an optical fiber amplifier. The present invention canbe applied to the preparation of a plastic optical fiber type amplifierand a thin film optical waveguide type amplifier by dispersing the rareearth metals therein in an organic polymer. More specifically, in thepast even with glass that was easier than an organic polymer to dopewith a rare earth metal, because quenching occurs more easily as thedoping concentration increases, optical amplifiers with a dopingconcentration of 100 ppm were realized by making them longer, but therewas a problem because they could not be made more compact; however, theorganic/inorganic composite containing a rare earth metal obtained bythe present invention can be applied to the manufacture of a compactoptical amplifier. In addition to the above industrial applications, thepresent invention can be applied to biosensors, color displays, lightemitting elements and the like that utilize the light emissionproperties of the rare earth metal/Period IV transition metal therein.In addition, by making use of the desirable feature of easyprocessability generally provide by an organic polymer, it becomespossible to apply objects of various shapes such as a thin film, sheet,fiber, compact, and the like to the aforementioned functions.

Objects having structures such as those shown in FIGS. 11( a) and (b)can be used as an optical waveguide in the optical amplifier of thepresent invention. Normally, FIG. 11( a) will be called a fiber type,and FIG. 11( b) will be called an optical waveguide type. In both cases,light is propagated while enclosed in a relatively highly refractivemember (core).

In the optical amplifier 3 the signal light 4 is propagated, andsimultaneously the excitation light 5 is also propagated. Normally, anoptical coupler is attached in front of and behind the opticalamplifier, and light is amplified by placing the excitation light on theoptical waveguide wherein the signal light 4 is propagated, or behindthe optical amplifier the excitation light 5 is isolated from thattransmission waveguide.

The optical waveguide of the present invention is formed by theorganic/inorganic composite containing a rare earth metal.

EXAMPLE 12 Preparation of Inorganic Dispersion Phase

Erbium acetate that had been dehydrated for 1 hour at 110° C. andtri-s-butoxy aluminum were added together in 2-butanol (Er/Al=3 molar,mathematically converted concentration of total oxides of Er and Al 5mass %) and refluxed for 1 hour to obtain a light pink transparentliquid. The particle size of the reaction product obtained thereby wasmeasured using dynamic light scattering, and it was confirmed that thereaction product comprised composite nanoparticles with a peak top of1.7 nm in diameter. In addition, coordination of the Al via an oxygenatom(s) with the Er was verified before and after the reaction withtri-s-butoxy aluminum by the change in 27Al-NMR spectrum.

<Preparation of Composite of Inorganic Dispersion Phase and TransparentOrganic Polymer>

A photopolymerizable acrylic resin “Cyclomer” (Daicel ChemicalIndustries, Ltd.) was used as the transparent organic polymer. Thisorganic polymer, the composite nanoparticles containing Er—Al preparedaccording to the above method, and a photoradical initiator “Irgacure369” (Ciba Specialty Chemicals) were mixed together in propylene glycolmonomethyl ether acetate (PGMEA), and stirred for 2 hours at roomtemperature to obtain a liquid mixture. The mixture ratio was controlledso that the erbium contents are 5.2% and 0.52% in mass in terms of solidcontent of the composite.

After a liquid mixture prepared in the above manner was rotary coated ona fused quartz plate using a spinner, the residual solvent was removedby drying for 1 minute on a plate heater at 90° C. to obtain a thin filmof organic/inorganic composite containing Er—Al and having an opticalpolymer acrylic resin as a matrix material. In addition, the thin filmwas exposed to light using an ultrahigh pressure mercury lamp via aphotomask wherein a 7 μm wide straight line waveguide pattern was drawn.Next the parts that were not exposed to the ultrahigh pressure mercurylamp were dissolved and removed by immersing the plate for 10 seconds inalkali water (2.3% aqueous solution of TMAH). Finally, after drying for2 minutes at 90° C., a 7 μm wide, 2.8 μm thick organic/inorganiccomposite waveguide comprising an optical polymeric acrylic resin and anEr—Al inorganic dispersion phase was obtained on the quartz plate.

<Measurement of Optical Amplifying Properties>

The optical amplifying properties of the organic/inorganic compositewaveguide comprising an optical polymeric acrylic resin and an Er—Alinorganic dispersion phase obtained thereby were measured using anoptics system such as that shown in FIG. 12. A 1550 nm wavelength, 3 mWcapacity semiconductor laser 6 was used as the light source for thesignal light 4, and a 983 nm wavelength, 150 mW peak capacitysemiconductor pulse laser 7 was used as the light source for theexcitation light 5. The excitation light 5 was superimposed onto theoptical axis of the signal light 4 using a dichroic mirror 8 having highreflectivity only near a wavelength of 980 nm, and joined at the end ofthe organic/inorganic composite waveguide 9 comprising a rare earthmetal wherein both lights were formed. In addition, to extract only thesignal light 4 and measure the intensity, after both lights werepropagated in the waveguide, the excitation light 5 was isolated with aprism 11 comprising SF6 glass by utilizing the principle that the angleof the outgoing beam differs according to the wavelength. Only thesignal light 4 that had passed through a pin hole 12 was received by aphotodetector 13 and the light intensity was measured using anoscilloscope.

As a result, it was confirmed that when the semiconductor pulse laserfor excitation light was lit, the signal intensity was amplified with again equivalent to 3.8 dB in comparison to when it was not lit, thusverifying the function of the present invention as an optical amplifier.

The present invention can be suitably used with respect to an opticalamplifier that amplifies the signal light intensity based on anexcitation light. EDFA wherein a quartz based inorganic material iscommercially used as a matrix material can be listed as an example ofsuch an optical amplifier, and in accordance with the present inventionthe quartz based inorganic material can be replaced with an organicpolymer, enabling the cost to be reduced thereby. In addition, becauserare earth metals, which could only be doped at a concentration of about50 to 100 ppm in the past, can now be doped at a concentration of 10%(100000 ppm) or more, the present invention enables the miniaturizationof optical amplifiers that could only be realized on a long scale in thepast. As a result, the optical amplifier of the present invention candisplay its effect not only in long distance, main line fiber optic netsthat have been used in the past, but also in applications such assubscriber optical communications nets and the like wherein the numberof downstream branches in the transmission waveguide increase and lossof optical transmission due to branching becomes a problem.

In addition, in the future the optical amplifier of the presentinvention can be displayed in the field of optical interconnectionswherein research is advancing to break the bottleneck in informationprocessing capacity and speed by using light rather than presently usedelectrons for transmission between and within circuit boards incomputers.

The light control optical element of the present invention is acollective term for optical elements having important functions ofcontrolling the transmission, refraction, focusing, scattering, and thelike of light in various optical equipments. Such a light controloptical element normally has a high transmittance value for visiblelight, but it can be used for the purpose of controlling thetransmittance or absorption of natural and various types of artificiallight such as light control glasses.

FIGS. 13( a) to 13(d) are explanatory diagrams that illustrate typicalexamples of the light control optical element of the present invention.In FIG. 13( a), the light control optical element is used in lenses foreyeglasses as lenses 21 a. In FIG. 13( b) the light control opticalelement is the cover 21 b used in various lighting devices (or lightingwindows). FIG. 13( c) is a diagram illustrating a lens 21 c (or window)used for goggles for industry such as for welding and the like, and usedin medical therapy and the like. FIG. 13( d) is a diagram of an opticalfilter 21 d wherein a light control optical element is used in atelevision receiver.

Among the lenses 21 a for eyeglasses shown in FIG. 13( a), a sunglasseslens is the most typical example of a light control optical element thatreduces the unpleasant sensation of glare by reducing the amount ofintense light. More specifically, sunglasses with a strong antiglareeffect can be obtained by reducing the amount of light with a wavelengthof 400 to 500 nm. Another application of lenses for eyeglasses arecorrective lenses for persons with a visual disorder wherein thediscrimination of colors is very difficult because they congenitallyhave a sensitivity curve that differs from the sensitivity curve of theeyes of normal individuals, and the corrective lenses adjust thetransmittance value of light to match the visual sensitivity of theperson with abnormal vision by selectively increasing the absorption oflight of specific wavelengths. Among the lighting windows or coversshown in FIG. 13( b), windows and covers with a strong antiglare effectcan be obtained by controlling the transmittance value of light inwavelengths of approximately 560 to 600 nm for light using halogen lampssuch as automobile headlights and the like.

The organic/inorganic composite containing a rare earth element or/andPeriod IV transition metal used in the light control optical element ofthe present invention is a composite of an organic polymer and a rareearth metal or/and Period IV transition metal that can be suitably usedin a light control optical element that controls the transmittance valueor absorption of light of a specific waveband, and concurrently controlstransmission, refraction, focus, scattering and the like, and itcomprises an organic polymer and an inorganic dispersion phase (rareearth metal or/and Period IV transition metal) wherein another metal iscoordinated thereto via an oxygen atom(s).

As the structure of the organic/inorganic composite containing a rareearth metal or/and Period IV transition metal used in the light controloptical element of the present invention, any combination may be usedprovided it is a composite containing a rare earth or/and Period IVtransition metal, a metal capable of coordinating with the rare earthmetal or/and Period IV transition metal via an oxygen atom(s), and anorganic polymer. The means for forming the inorganic dispersion phasewherein the other metal coordinates with the rare earth metal or/andPeriod IV transition metal via an oxygen atom(s) is not particularlylimited, and may be formed, for example by the reaction of a rare earthmetal salt and a metal alkoxide.

The composite of the organic polymer and the inorganic dispersion phasewherein coordination of the rare earth metal or/and Period IV transitionmetal with the other metal occurs via an oxygen atom(s) can, forexample, be prepared by mixing the inorganic dispersion phase formed bythe reaction of the aforementioned metal alkoxide and the rare earthmetal salt or/and Period IV transition metal salt together with theorganic polymer and dispersing the same therein.

EXAMPLE 13 Preparation of the Organic Dispersion Phase

Neodymium acetate that had been dehydrated under vacuum for 1 hour at110° C. and tri-s-butoxy aluminum were added together in propyleneglycol α-monomethyl ether (Nd/Al=3 molar, mathematically convertedconcentration of total oxides of Nd and Al 5 mass %) and refluxed for 1hour to obtain a light purple transparent liquid. The particle size ofthe reaction product obtained thereby was measured using dynamic lightscattering, and it was confirmed that the reaction product comprisedcomposite nanoparticles with a peak top of 2.3 nm in diameter. Inaddition, coordination of the Al via an oxygen atom(s) with the Nd wasverified before and after the reaction with tri-s-butoxy aluminum by thechange in 27Al-NMR spectrum.

<Preparation of Composite of Inorganic Dispersion Phase and TransparentOrganic Polymer>

Hydroxypropyl cellulose (Nippon Soda Co., Ltd.) was used as thetransparent organic polymer. This organic polymer and the compositenanoparticles containing NdAl prepared according to the above methodwere mixed together in Ethyl Cellosolve, and stirred for 2 hours at roomtemperature to obtain a liquid mixture. The mixture ratio was controlledso that the neodymium (Nd) content is 8% in mass in terms of solidcontent of the composite.

The liquid mixture formulated as noted above was poured into apolytetrafluoroethylene container used as mold, and an approximately 1mm thick cast molded product of the organic/inorganic compositecontaining Nd was obtained by evaporating the Ethyl Cellosolve at 120°C. and drying.

<Measurement of Spectroscopic Absorption Properties>

The spectroscopic absorption properties of the organic/inorganiccomposite containing Nd obtained thereby was measured using aspectrophotometer. FIG. 3 shows the spectroscopic absorption spectrum ofthe composite nanoparticles containing Nd—Al/hydroxypropyl cellulosecomposite prepared according to the above method. It is clear thatabsorption in the wavebands of approximately 500 to 540 nm andapproximately 560 to 600 nm originating from the Nd absorption can beassured in the composite nanoparticles containing Nd—Al/hydroxypropylcellulose composite.

<Fabrication of a Window for Lighting>

In accordance with the aforementioned method of preparing theorganic/inorganic composite containing Nd, a coating layer of theorganic/inorganic composite containing Nd was formed on the cover for ahalogen lamp that is widely used. It was confirmed that when this coverwas used, the glare specific to halogen lamps was reduced, and such acover will be effective as an automobile headlight and the like.

EXAMPLE 14 Preparation of the Inorganic Dispersion Phase

Praseodymium acetate that had been dehydrated for 1 hour at 110° C. andtri-s-butoxy aluminum were added together in propyleneglycol-α-monomethyl ether (Pr/Al=3 molar, mathematically convertedconcentration of total oxides of Pr and Al 5 mass %) and refluxed for 1hour to obtain a light green transparent liquid. The particle size ofthe reaction product obtained thereby was measured using dynamic lightscattering, and it was confirmed that the reaction product comprisedcomposite nanoparticles with a peak top of 6.5 nm in diameter. Inaddition, coordination of the Al via an oxygen atom(s) with the Pr wasverified before and after the reaction with tri-s-butoxy aluminum by thechange in 27Al-NMR spectrum.

<Preparation of Composite of Inorganic Dispersion Phase and TransparentOrganic Polymer>

A photopolymerizable acrylic resin “Cyclomer” (Daicel ChemicalIndustries, Ltd.) was used as the transparent organic polymer. Thisorganic polymer, the composite nanoparticles containing PrAl preparedaccording to the above method, and a photoradical initiator “Irgacure369” (Ciba Specialty Chemicals) were mixed together in PGMEA, andstirred for 2 hours at room temperature to obtain a liquid mixture. Themixture ratio was controlled so that the praseodymium (Pr) content is10% in mass in terms of solid content of the composite.

Using a polytetrafluoroethylene container as a mold, an approximately 1mm thick transparent cast molded product of the organic/inorganiccomposite containing Pr was obtained by evaporating the PGMEA at 120° C.and drying.

<Measurement of Spectroscopic Absorption Properties>

The spectroscopic absorption properties of the organic/inorganiccomposite containing Pr obtained thereby was measured using aspectrophotometer. The spectroscopic absorption spectrum of thecomposite nanoparticles containing Pr—Al/photopolymerizable acrylicresin composite prepared according to the above method was the same asthat of FIG. 9 shown in EXAMPLE 10. It is clear that absorption in thewavebands of approximately 440 to 490 nm originating from the Prabsorption can be assured in the composite nanoparticles containingNi—Nb/photopolymerizable acrylic resin composite.

<Preparation of Lens>

A lens was prepared in accordance with the method for preparing theaforementioned organic/inorganic composite containing Pr. It wasconfirmed that this lens is suitable as an antiglare lens because theabsorption thereby of blue-green light components is selectively high.

EXAMPLE 15 Preparation of the Inorganic Dispersion Phase

Nickel acetate that had been dehydrated for 1 hour under vacuum at 100°C. and pentaethoxy niobium were added together in ethylene glycolmonomethyl ether (Ni/Nb=2 molar, mathematically converted concentrationof total oxides of Ni and Nb 5 mass %) and refluxed for 1 hour to obtaina green transparent liquid. The particle size of the reaction productobtained thereby was measured using dynamic light scattering, and it wasconfirmed that the reaction product comprised composite nanoparticleswith a peak top of 2.9 nm in diameter.

<Preparation of Composite of Inorganic Dispersion Phase and TransparentOrganic Polymer>

The photopolymerizable resin “Cyclomer” ((Daicel Chemical Industries,Ltd.) was used as the transparent organic polymer in accordance withEXAMPLE 2. This organic polymer and the composite nanoparticlescontaining Ni—Nb prepared according to the above method were mixedtogether in Ethyl Cellosolve, and stirred for 2 hours at roomtemperature to obtain a liquid mixture. The mixture ratio was controlledso that the Ni content is 8% in mass in terms of solid content of thecomposite.

The liquid mixture formulated as noted above was poured into apolytetrafluoroethylene container used as mold, and an approximately 1mm thick transparent cast molded product of the organic/inorganiccomposite containing Nb was obtained by evaporating the Ethyl Cellosolveat 120° C. and drying.

<Measurement of Spectroscopic Transmittance Value>

The spectroscopic absorption properties of the organic/inorganiccomposite containing Ni obtained thereby was measured using aspectrophotometer. The spectroscopic absorption spectrum of thecomposite nanoparticles containing the Ni—Nb/hydroxypropyl cellulosecomposite prepared according to the above method was the same as that ofFIG. 10 shown in EXAMPLE 11. It is clear that absorption in thewavebands of approximately 900 to 600 nm and approximately 450 nm orless originating from the Ni absorption can be assured in the compositenanoparticles containing Ni—Nb/hydroxypropyl cellulose composite.

Based on the above results the present invention makes it possible toprovide an organic/inorganic composite wherein a rare earth metal or/andPeriod IV transition metal is doped at a high concentration in anorganic polymer, and the original absorption properties of the dopingelements can be expressed thereby.

<Preparation of Lens>

A lens was prepared in accordance with the method for preparing theaforementioned organic/inorganic composite containing Ni. It wasconfirmed that this lens is suitable as an antiglare lens because theabsorption thereby of blue-green to UV light components is selectivelyhigh.

The present invention can be used in a light control optical elementthat is used for controlling the transmittance and absorption of lightof a specific wavelength or waveband, and it can assume manyadvantageous forms in accordance with the needs thereof.

A light control lens can be listed as an example thereof. More specificexamples of applications include sunglasses, antiglare lenses, lensesfor persons with visual abnormalities, goggles for industrial welding(protective eyeglasses), goggles used in medical therapy, and the like.

Enclosures for various light sources, window materials and the like canalso be listed as applications of the present invention. More specificexamples include window material for automobile headlights and variouspoint light sources, and lens cover materials and the like.

With respect to lighting such as various EDT lights and reflector lampsand the like that are widely used in general households, the presentinvention can be used to control the spectrum of the lamplight extractedby applying the present invention to decorative windows and the like.For example, it is possible to control color rendering by attenuatingthe blue components in a white fluorescent light to create a warm colortone and the like.

The present invention can be applied as a material for industrialwindows and building windows having a filter effect using transparentpolymer material, or as a display filter for television and the like.For example, by doping with a rare earth metal such as neodymium thatselectively absorbs light in the red band, the present invention canbecome a window material having a heat ray attenuating effect.

The luminescent device of the present invention is equipped with a lightemitting element and a rare earth luminescence material. The rare earthluminescence material can be any combination provided it is a compositecomprising a rare earth metal, a metal capable of coordinating with therare earth metal via an oxygen atom(s), and an organic polymer.

The means of forming the organic dispersion phase wherein another metalcoordinates with the rare earth metal via an oxygen atom(s) is notparticularly limited and for example, the organic dispersion phase maybe formed by the reaction of a rare earth metal salt and a metalalkoxide.

The composite of the organic polymer and the inorganic dispersion phasewherein coordination of the rare earth metal with the other metal occursvia an oxygen atom(s) can, for example, be prepared by mixing theinorganic dispersion phase formed by the reaction of the aforementionedmetal alkoxide and the rare earth metal salt together with the organicpolymer and dispersing the same therein.

[Light Emitting Element]

Items generally called electric bulbs, EDT fluorescent lamps, LEDs andthe like can be used as the light emitting element.

Examples of electric bulbs include not only incandescent bulbs whereinelectric current flows through a filament to heat it, and then light isdischarged as thermal radiation, but also krypton lamps wherein kryptongas is sealed within the electric bulb, halogen lamps that utilize thehalogen cycle, and the like.

Examples of EDT fluorescent lamps include not only the most generalfluorescent lamp using mercury discharge, but also black lights thatemit only UV light in the same manner.

High intensity discharge lamps (HID lamps) are also items that emitfluorescent light by the collision of electrons generated from anelectrode similar to that in an EDT fluorescent lamp and mercury vaporsealed in the lamp, but because the density of mercury atoms duringignition and the temperature are much higher than in a conventionalfluorescent lamp, they are often classified separately from fluorescentlamps. As a group of these HID lamps, sodium lamps, metal halide lamps,mercury lamps, and the like can be used as the light emitting element inthe present invention.

LEDs are light emitting elements utilizing various semiconductors, andobtained by forming pn junctions. Known examples of semiconductorsinclude gallium-arsenide, gallium phosphide,aluminum-gallium-indium-fluorescent materials,indium-gallium-arsenic-fluorescent materials, zinc selenide, zincsulfide, indium sulfide, zinc-sulfur-selenium, gallium nitride,indium-gallium-nitrogen, silicon carbide, and the like but are by nomeans limited to the same. Semiconductor lasers wherein thesesemiconductors are formed into a structure capable of laser excitationcan be sued as the light emitting element of the present invention.

Examples of light emitting elements that can be used in the presentinvention have been presented above, but the light emitting element ofthe present invention is not particularly limited provided it is onethat can convert electric energy to light energy.

[Rare Earth Metal Luminescence Material]

The term rare earth metal luminescence material refers to rare earthmetal atoms alone, or a rare earth metal complex or molecular clustercontaining a rare earth metal wherein a specific molecule or group ofmolecules is coordinated thereto for the purpose of increasing thestability and solubility/dispersibility of the rare earth metal atoms.

Luminescence material that is generally used is one wherein a targetsubstance is attached by a method such as sputtering in which a bulkbody is initially formed, said bulk body being one in which a rare earthmetal is doped into transparent oxide crystals such as Y₃Al₅O₁₂ (YAG),YLiF₄ (YLF), YVO₄, and the like, or into glass such as silicate glass,phosphate glass, fluoride glass, and the like during the crystal growingprocess or glass forming process, and then the bulk body is pulverizedand kneaded into an organic material, and the bulk body is used as atarget for sputtering. Recently, a method for obtaining fine particleswithout pulverization has been adopted wherein doping of the rare earthmetal is performed during the growth process of the aforementionedtransparent crystals of nanometer size by a sol-gel process and thelike.

In any event, with respect to the problem of doping a rare earth metalinto an organic medium which is the object of this application, in orderto distinguish prior art methods wherein the rare earth metal istemporarily supported on a material that can easily incorporate a rareearth metal such as the aforementioned transparent crystals or glass andthe like, and then kneaded into an organic medium, from a processwherein a rare earth complex or a molecular cluster containing a rareearth metal in which another molecule or group of molecules iscoordinated to the rare earth metal is doped directly into the organicmedium, the former shall be defined as a fluorescent material, and thelatter as a rare earth metal luminescence material.

EXAMPLE 16 Preparation of Composite of Inorganic Dispersion Phase andTransparent Organic Polymer

The Eu—Al luminescence material, Tb—Al luminescence material, and Ce—Alluminescence material prepared in EXAMPLE 3, 5, and 8, respectively weremixed in Ethyl Cellosolve and stirred for 2 hours to obtain a liquidmixture. The mixture ratio was controlled so that the respective ratiosof Eu, Tb, and Ce in the composite nanoparticles would be 5% of thetotal solids.

The liquid mixture formulated as noted above was poured into apolytetrafluoroethylene container used as mold while evaporating anddrying the Ethyl Cellosolve at 120° C. or less, and an approximately 1mm thick cast molded product of the organic/inorganic compositecontaining Eu, Tb, and Ce was prepared on a glass panel.

<Preparation of Luminescent Device>

An LED emitting UV light at a wavelength of 380 nm was mounted on aprinted board as a light emitting element, and connected to a 6 V DCpower source via a 330Ω resistance to prepare a light emitting unit.After this light emitting unit was enclosed in an aluminum enclosure,and the cast molded products of the organic/inorganic compositecontaining the Eu—Al luminescence material, Tb—Al luminescence material,and Ce—Al luminescence material prepared in the above manner were fittedto form a window. Thereby a luminescent device using the UV light LED asa light emitting element, and having a window wherein the cast moldedproduct of the organic/inorganic composite containing Eu—Al, Tb—Al, andCe—Al was formed on glass plate. When current was applied to thisluminescent device, white light was observed. In addition when theemitted color was measured with a spectroscope, an emission spectrumsuch as that shown in FIG. 15 was obtained. When a CIE chromaticitydiagram was prepared using the emission spectrum shown in FIG. 15, achromaticity diagram such as that shown in FIG. 16 was obtained. It wasconfirmed that the emitted color of these Examples represented by thecolor display chart was white, and this device was effective as a whitelight emitting element.

The present invention is suitably used in a luminescent device whereinelectric energy is converted to light energy. Examples of such aluminescence device include LED elements of various colors, and lightingdevices utilizing the same. It is known that by selecting the materialof the semiconductor various emission colors can be obtained in the LEDper se, but depending on the field of use, different color renderingproperties are needed. For example, in a white LED obtained by excitinga YAG fluorescent material by a blue LED, the overall paleness standsout. There is a problem when such a luminescence device is used forlighting in medical therapy because it cannot be accurately determinedwhether the color of blood is normal or not. The above problem can besolved in such a case by doping an LED sealing resin with the compositenanoparticles containing Eu—Al obtained in the present invention, whichwill not only attenuate the paleness by the accompanying Eu absorption,but also add light emission in the red band from Eu.

In addition, such an LED can be used in a modular, large flat displaydevice. More specifically, there has not been an LED in such a displaythat emits suitable green light in the past, and the display could notperform sufficiently as an RGB color display. However, the above problemcan be solved by doping a UV LED sealing resin with compositenanoparticles containing Tb—Al obtained in the present invention, and agreen LED with superb color emitting properties can be obtained thereby.

The invention claimed is:
 1. An organic/inorganic composite comprisingan inorganic dispersion phase dispersed in an organic polymer, theinorganic dispersion phase comprising one or more metal atoms that arecoordinated to at least one rare earth metal atom via oxygen; andwherein the composite contains at least 5 mass % of rare earth metal,wherein the rare earth metal is dispersed in said inorganic dispersionphase.
 2. The organic/inorganic composite of claim 1 wherein the one ormore metal atoms are selected from the group consisting of aluminum,gallium, titanium, zirconium, niobium, and tantalum.
 3. Theorganic/inorganic composite of claim 2 wherein the one or more metalatoms are selected from Group 3B, Group 4A or Group 5A of the periodictable.
 4. The organic/inorganic composite of claim 2 wherein the oxygenbridging at least one rare earth metal atom and one or more metal atomsis an —O(R)— moiety wherein R comprises an alkyl group, reactive vinylgroup, aryl group, diazo group, nitro group, cinnamoyl group, acryloylgroup, imide group, epoxy group, cyano group, or an alkyl group, alkylsilyl group, or alkyl carbonyl group with (b) a polymer or polymerprecursor.
 5. The organic/inorganic composite of claim 2 wherein thewherein the at least one rare earth metal comprises Eu, Tb, and Ce.
 6. Aluminescent device comprising the organic/inorganic composite of claim2.